Herbicidal aryl triazolinones

ABSTRACT

Herbicidal aryl triazolinones include the compounds of the formula ##STR1## where X is preferably halogen such as fluorine, Y is preferably halogen such as chlorine, R 1  is preferably methyl, R 2  is preferably CHF 2 , R 3  is preferably CH(CH 3 ), and ##STR2## is --NH 2  or the residue of a primary or secondary amine or of a sulfonamide.

This application is a continuation-in-part of my application Ser. No.807,382, filed Dec. 10, 1985 now abandoned, a continuation-in-part of mycopending application of the same name, filed Oct. 21, 1985, Ser. No.824,696 still pending whose entire disclosure is incorporated herein byreference, and a continuation-in-part of Ser. No. 666,933, filed Oct.31, 1984 now abandoned.

The invention described in this application pertains to weed control inagriculture, horticulture, and other fields where there is a desire tocontrol unwanted plant growth. More specifically, the presentapplication describes certain herbicidal aryl triazolinones,compositions of them, methods of preparing them, and methods forpreventing or destroying undesired plant growth by preemergence orpostemergence application of the herbicidal compositions to the locuswhere control is desired. The present compounds may be used toeffectively control a variety of both grassy and broadleaf plantspecies. The present invention is particularly useful in agriculture; anumber of the compounds described herein show a selectivity favorable tocorn and cereal crops such as wheat, upland rice and paddy rice atapplication levels which inhibit the growth of or destroy a variety ofweeds.

One aspect of this invention relates to herbicidal compounds of thegeneral formula ##STR3## in which R³ is an alkylene radical (e.g. --CH₂-- or --CH(CH₃)--) or a haloalkylene radical (e.g. --CHF--), and##STR4## is --NH₂ or the residue or a primary or secondary amine or of asulfonamide. For instance, R⁶ and R⁷ may be, each, independently, H,alkyl, alkenyl, alkynyl, cycloalkyl, aryl heterocyclic such as pyrimidyl(e.g. 2-pyrimidyl), triazinyl or pyridinyl, alkoxy, alkylsulfonyl,haloalkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl (includingheteroarylsulfonyl such as isoxazolylsulfonyl, thienylsulfonyl),aralkylsulfonyl, aminosulfonyl, dialkylaminosulfonyl,alkylthioalkylsulfonyl (e.g. CH₃ SCH₂ SO₂ --),alkylsulfonylalkylsulfonyl (e.g. CH₃ SO₂ CH₂ SO₂ --),alkylaminosulfonyl, alkenylsulfonyl, phenylalkenylsulfonyl. R⁶ may bebicyclic or polycyclic such as benzofuranyl, dihydrobenzofuranylbenzofuransulfonyl, dihydrobenzofuransulfonyl, naphthalenesulfonyl,benzodioxolsulfonyl, anthraquinonesulfonyl or1,4-naphthoquinonesulfonyl. Any of R⁶ and R⁷ may carry one or moresubstituents such as halogen, nitro, amino, fluorosulfonyl, alkyl,haloalkyl, aminoalkyl, dialkylaminoalkyl, haloalkoxy, alkoxy,alkenyloxy, haloalkenyloxy, alkynyloxy, cyanoalkoxy, epoxyalkoxy,dialkylaminoalkoxy, alkoxyalkoxy, alkoxyalkylthio, cyano,aminocarbonyloxy, alkylaminocarbonyloxy, dialkylaminocarbonyloxy,acylamino, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl or hydroxycarbonyl (but when one of R⁶, R⁷ isconnected to the nitrogen of formula I by an oxygen or sulfur atom, thenthe other of R⁶, R⁷ is H or a group connected to that nitrogen by acarbon-nitrogen linkage or a salt-forming group, such as indicatedbelow); for instance, when R⁶ is arylsulfonyl, the aryl radical of R⁶may be an unsubstituted phenyl or naphthyl or may be a phenyl ornaphthyl carrying one or more of the foregoing substituents, with anyalkyl portion of a substituent having, for instance, 1 to 4 carbonatoms. R⁶ and R⁷ may together comprise a divalent group, such as analkylene or haloalkylene or alkyloxyalkylene group or thioether, or itscorresponding sulfine or sulfone, (e.g. such that NR⁶ R⁷ togethercomprise a pyrrolidino, piperidino, morpholino, or thiazolidino ring),any of which may also carry a carboxylic ester or amide substituent. Thesalt-forming group (e.g. when R⁶ is alkylsulfonyl, cycloalkylsulfonyl orarylsulfonyl) may be a metal (e.g. Na, K or Ca) or ammonium (e.g. NH₄ orlower alkyl-substituted ammonium). R⁶ and R⁷ may comprise a divalentgroup such that NR⁶ R⁷ together constitute, for instance, a saccharinring structure, e.g. ##STR5## which is an active herbicide (such ascompound C62 below) and which upon hydrolysis, can lead to other activeherbicides such as compounds C58 and C59.

Compound C62 for example is obtainable by reaction of saccharin ##STR6##with the appropriate acid chloride.

In this (Formula I) aspect of the invention, X, may be bromine,chlorine, fluorine or haloalkyl (e.g. CF₃);

R¹ may be halogen (e.g. chlorine), alkyl (e.g. of 1 to 5 carbon atoms),haloalkyl (e.g. of 1 to 5 carbon atoms such as difluoromethyl),alkoxyalkyl (e.g. of 2 to 6 carbon atoms such as methoxymethyl),cyanoalkyl (e.g. of 2 to 6 carbon atoms such as cyanomethyl), arylalkylsuch as benzyl, alkylthio (e.g. of 1 to 3 carbon atoms such asmethylthio) or the corresponding alkylsulfinyl or alkylsulfonyl, oralkylthioalkyl (e.g., of 1 to 3 carbon atoms independently with respectto each alkyl, such as methylthiomethyl) or the correspondingalkylsulfinylalkyl or alkylsulfonylalkyl;

Y may be bromine, chlorine, fluorine, methyl, haloalkyl (e.g. FCH₂), aradical of the formula R⁸ OCH₂ --, R⁸ SCH₂ --, R⁸ SOCH₂ -- or R⁸ SO₂ CH₂-- where R⁸ is C₁ -C₃ alkyl, C₂ -C₅ alkenyl, or C₃ -C₅ alkynyl (e.g.,CH₃ OCH₂ --, CH₃ SCH₂ --, CH₂ ═CHCH₂ OCH₂ --, CH₂ ═CHCH₂ SCH₂ --,CH.tbd.CCH₂ OCH₂ --, or CH.tbd.C--CH₂ SCH₂ --); R₈ may also be phenyl(or phenyl substituted with e.g., halogen, alkyl, haloalkyl);

R² may be alkyl (e.g. of 1 to 5 carbon atoms), haloalkyl (e.g. of 1 to 5carbon atoms such as CHF₂ or CH₂ F), alkenyl of 2 to 5 carbon atoms(e.g. allyl), alkynyl of 3 to 5 carbon atoms (e.g. propargyl),cyanoalkyl (e.g. CH₂ CN or CH₂ CH₂ CN), thiocyanoalkyl (e.g. CH₂ SCN) ora group of the formula --alkylene--Y¹ --R⁵ in which said alkylene group(e.g. --CH₂ --) has 1 to 5 carbon atoms, Y¹ being oxygen or S(O)_(r) inwhich r is 0 to 2, and R⁵ being alkyl (e.g. of 1 to 5 carbon atoms suchas methyl), alkenyl of 2 to 5 carbon atoms (e.g. allyl) or alkynyl of 3to 5 carbon atoms (such as propargyl).

In each aspect of the invention, it is often preferable that any alkyl,alkenyl, alkynyl or alkylene radical have less than 6 carbon atoms.

Representative compounds according to the invention are shown in Table 1below.

The compounds of this invention are preferably those whose MethoxyAnalog or Propargyloxy Analog is a herbicide. The term "Methoxy Analog"is used here to designate a compound which is otherwise identical exceptthat it has a methoxy group instead of the ##STR7## group of saidcompound. The term "Propargyloxy Analog" is similarly used here for acompound which is otherwise identical except that it has a propargyloxygroup instead of the ##STR8## group of said compound.

The compounds of this invention preferably have Methoxy Analogs andPropargyloxy Analogs of marked herbicidal properties. For instance saidAnalogs of the preferred compounds show at least 50% kill of at leastone of the following species of plants when applied under at least oneof the following modes at the rate of 0.5 kg/ha, and more preferablyshow such kill of at least 50% when applied at the rate of 0.1 kg/ha:Species velvetleaf (Abutilon theophrasti), green foxtail (Setariaviridis); Modes: pre-emergent, post-emergent. Testing for suchherbicidal activity may be carried out in the manner described below(under the heading "Herbicidal Activity").

The compounds of this invention may be prepared by methods generallydescribed in the literature or by methods analogous or similar theretoand within the skill of the art. One type of method starts with anintermediate in which the substituent para to "X" is hydroxyl. Forinstance, one may use the intermediate described in "Synthetic ProcessExample 6" of UK patent application GB No. 2 090 250 published 7 July1982, in which X and Y are Cl, R¹ is CH₃ and R² is CHF₂ (thecorresponding compound in which R² is CH₂ F is made by substitutingchlorofluoromethane for the chlorodifluoromethane used in "SyntheticProcess Example 1" of that published patent application). The OH groupof the intermediate may then be converted to the desired substituent, asby a conventional etherification reaction, e.g., by reacting it with theappropriate bromide in the presence of a known acceptor of HBr such asNaH or a mixture of K₂ CO₃ and NaI.

As illustrated in Example 2 below, the synthesis may employ asubstituted phenylhydrazine, whose hydrazine portion is then modified toform a triazolinone ring. Such modification (which in Example 2 iseffected by reaction with pyruvic acid and then with a phosphoryl azide)may also be effected by other techniques, such as by treating thesubstituted phenylhydrazine with any of the following four types ofreagents:

(a) an inner salt of a 3-(1-iminoalkylmercapto)-1-propanesulfonic acid(which may be prepared according to Reid and Schmidt, Ann. Chem. 676,114 (1964) from 1,3-propanesultone and a thioamide), to form anamidrazone followed by reaction with a source of phosgene, as by thefollowing reaction sequence (which is also illustrated in Example 7below), ##STR9## in which "Ar" is aromatic as described below.

(b) An imidate ester of the formula ##STR10## to form the correspondingamidrazone (as described, for instance, in the article by Neilson et al"The Chemistry of Amidrazones: Chem. Rev. 70, 151(1970) at page 156),followed by reaction with a source of phosgene, as in (a) above, R^(c)and R^(d) being alkyl or other suitable radical.

(c) A compound of the formula ##STR11## (where R^(a) and R^(b) are loweralkyl) in the presence of a base according to the following sequence:##STR12## in which R¹ is as defined above, e.g. methyl;

(d) A haloalkylnitrile (e.g. a fluoroalkyl, fluorochloroalkyl orfluorobromoalkyl nitrile such as ClCF₂ CN, followed by reaction with asource of phosgene, so that the reaction may proceed along the followinglines, for instance (and as also illustrated in Example 8 below), toform the aryl 3-haloalkyl triazoline, thus: ##STR13##

In Example 2 below the "Ar" portion of the aryl hydrazine (whosehydrazine portion is then modified to form the triazoline ring) has halosubstituents at its 2 and 4 positions and an alkoxy group at its 5position. Instead, in each of the processes illustrated above (and inthe process of Example 2), the Ar group may be a phenyl radical or afluorophenyl (e.g. 2-fluorophenyl) or a nitrophenyl (e.g. 3-nitrophenyl)alkoxyphenyl (e.g. 3-methoxyphenyl) or, most preferably,halonitrophenyl, particularly a fluoronitrophenyl (such as2-fluoro-5nitrophenyl) or haloalkoxyphenyl (such as2-fluoro-5alkoxyphenyl) and the aryl triazoline may then be treated to(a) alkylate the nitrogen at the 4-position of the triazoline ring (inknown manner, e.g. with an alkyl or fluoroalkyl halide, such as withClCHF₂ to add the preferred --CHF₂ substituent) and (b) to introduceadditional substituents onto the aromatic ring, as by halogenation withchlorine or bromine (e.g. by reacting with Cl₂, Br₂ or SO₂ Cl₂). Forinstance the alkylation of the nitrogen at the 4-position may beeffected first, after which the nitro group (if present) may be reducedto an amino group in conventional manner, the amino group may beconverted to a hydroxyl group (as by conventional diazotization) andthen, preferably after etherifying the OH to form an alkoxy (e.g.methoxy) group, the compound may be halogenated as above to place thehalogen substituent or substituents on its benzene ring. The resultingcompound may then be modified at the 5-position of the benzene ring toform the herbicidal compounds of this invention. For instance, formaking the preferred compounds of the invention in which the benzenering has a 2-fluoro substituent, the starting material may be2-fluoro-5-nitrophenylhydrazine, which may be treated as described aboveto produce successively a series of novel compounds such as1-(2-fluoro-5-nitrophenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one,then1-(2-fluoro-5-nitrophenyl-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one.These may be converted to the corresponding novel compounds having, atthe 5-position of the benzene ring, successively --NH₂, --OH and(preferably) --OCH₃, followed by halogenation to place, for instance, achloro or bromo substituent at the 4-position of the benzene ring.Instead of alkylating at the 4-position of the ring triazoline at anearly stage, e.g. prior to altering the nitro group, this alkylationstep may be delayed until after the abovedescribed halogenation of thebenzene ring or even until after the conversion of the alkoxy (or other)group at the 5-position of the benzene ring to one of the groupsdescribed at that position in Formula I.

Similarly, when the reagent(s) used to react with the aryl hydrazine aresuch as to produce a triazolinone having a haloalkyl (e.g. CHF₂) groupinstead of an alkyl group on the carbon at the 3-position of theheterocyclic ring, the series of new compounds will include,successively, (from 2-fluoro-5-nitrophenyl hydrazine) such compounds as1-(2-fluoro-5-nitrophenyl)-4,5-dihydro-3-difluoromethyl-1,2,4-triazol-5-(1H)-one,then 1-(2-fluoro-5-nitrophenyl)-4,5-dihydro-4-methyl (ordifluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one. These may beconverted to the corresponding novel compounds having, at the 5-positionof the benzene ring, successively --NH₂, --OH and (preferably) --OCH₃followed by halogenation to place, for instance, a chloro or bromosubstituent at the 4-position of the benzene ring. When the arylhydrazine is 3-nitrophenyl hydrazine (instead of2-fluoro-5-nitrophenylhydrazine) the series of novel compounds willinclude, successively, such compounds as1-(3-nitrophenyl)-4,5-dihydro-3-difluoromethyl-1,2,4-triazol-5(1H)-one,then 1-(3-nitrophenyl)-4,5-dihydro-4-methyl (ordifluoromethyl)-3-difluoromethyl-1,2,4-triazol-5(1H)-one. These may beconverted to the corresponding novel compounds having, at the 3-positionof the benzene ring, successively --NH₂, --OH and (preferably) --OCH₃,followed by halogenation to place, for instance, chloro or bromosubstituents on the benzene ring.

Example 4 below illustrates a process for making a compound of thisinvention having a sulfonamide group at the 5-position of the benzenering by reacting (a) a compound having an oxypropionic acid substituentat that 5-position with (b) an aryl sulfonylisocyanate.

Another method for introducing the sulfonamide group is by reacting (a)a compound having a phenolic OH group at that 5-position with (b) anN-aryl (or alkyl etc.) sulfonylalkanoic acid amide having a reactiveleaving substituent (e.g. Br, Cl, mesylate or tosylate) on the alkaneportion of the molecule, e.g. ##STR14## Such a reaction can be carriedout in the presence of a base (e.g. in acetone in the presence of sodiumor potassium carbonate). This method is illustrated in Example 6 below.

The following Examples illustrate the preparation of the compounds ofthis invention.

EXAMPLE 1Ethyl[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]acetate

To a stirred mixture of 15.0 g (0.048 mole) of1-(2,4-dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneand 3.4 g (0.024 mole) of potassium carbonate in 100 mL of acetone wasadded 8.1 g (0.048 mole) of ethyl bromoacetate. The resultant mixturewas stirred at reflux for three hours. After cooling, the mixture wasevaporated under reduced pressure leaving a residue. This residue waspartitioned between diethyl ether and water. The organic phase waswashed with an aqueous 10% sodium hydroxide solution, then was driedover anhydrous magnesium sulfate and filtered. Evaporation of thefiltrate under reduced pressure produced 17.8 g of a solid. A smallportion of this solid was recrystallized from methanol and water toyieldethyl[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]acetate(mp 118°-119° C.), compound 17.

The nmr spectrum was consistent with the proposed structure.

The following compounds were also prepared by the process of Example 1from1-(2,4-dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid, compound A1; or2-[4-chloro-2-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid, compound A2, and one of the following:

    ______________________________________                                        Compound       Reagent                                                        ______________________________________                                        14             methyl bromoacetate                                            17             ethyl bromoacetate                                             19             tert-butyl 2-bromopropionate                                   21             tert-butyl bromoacetate                                        22             tert butyl bromoacetate                                        B6             1-methyl-2-propynyl                                                           2-bromopropionate                                              B7             1,1-dimethyl-2-propynyl                                                       2-chloropropionate                                              B11           bromoacetonitrile                                               B16           α-bromo-γ-butyrolactone                             B22           chloromethyl methylether                                        B23           chloromethyl methylsulfide                                     C1             iodoacetamide                                                  C7             iodoacetamide                                                  C9             N--(1-methylpropyl)                                                           2-bromopropionamide                                            ______________________________________                                    

EXAMPLE 22-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid

Step A: 4-Chloro-2-fluoro-5-methoxyaniline from 2-chloro-4-fluorophenol

The intermediate 4-chloro-2-fluoro-5-methoxyaniline was prepared in afive step synthesis from commercially available 2-chloro-4-fluorophenolas detailed by E. Nagano, et al. in European Patent Application No.69,855.

Step B: 4-Chloro-2-fluoro-5-methoxyphenylhydrazine

A stirred solution of 48.0 g (0.27 mole) of4-chloro-2-fluoro-5-methoxyaniline in 500 mL of concentratedhydrochloric acid was cooled to -5° C. and 23.5 g (0.34 mole) of sodiumnitrite in 100 mL of water was added dropwise. After complete additionthe reaction mixture was stirred at 0° C. for one hour. A secondsolution of 154.0 g (0.68 mole) of stannous chloride in 225 mL ofconcentrated hydrochloric acid was cooled to 0° C., and the colddiazonium solution prepared above was added to it slowly. After completeaddition the reaction mixture was allowed to warm to ambienttemperature. The reaction mixture was filtered to collect a solid. Thissolid was dissolved in an aqueous 50% sodium hydroxide solution and thesolution extracted with toluene. The toluene extract was dried withmagnesium sulfate and filtered. The filtrate was concentrated underreduced pressure to yield 22.4 g of4-chloro-2-fluoro-5-methoxyphenylhydrazine as a solid.

The nmr spectrum was consistent with the proposed structure.

Step C: Pyruvic acid, 4-chloro-2-fluoro-5-methoxyphenylhydrazone

A stirred solution of 21.0 g (0.11 mole) of4-chloro-2-fluoro-5-methoxyphenylhydrazine and 100 mL of aqueous 10%hydrochloric acid in 100 mL of ethanol was warmed to 40° C., and asolution of 10.0 g (0.114 mole) of pyruvic acid in 20 mL of water wasadded. Upon complete addition the reaction mixture was stirred for onehour. An additional 50 mL of water was added and the reaction mixturefiltered to collect a solid. The solid was air dried to yield 29.0 g ofpyruvic acid, 4-chloro-2-fluoro-5-methoxyphenylhydrazone; mp 166°-169°C.

The nmr spectrum was consistent with the proposed structure.

Step D:1-(4-Chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

A stirred solution of 27.0 g (0.104 mole) of pyruvic acid,4-chloro-2-fluoro-5-methoxyphenylhydrazone, 29.0 g (0.105 mole) ofdiphenyl phosphoryl azide, and 11.0 g (0.108 mole) of triethylamine in500 mL of toluene was heated under reflux for four hours. The reactionmixture was cooled to ambient temperature and extracted with an aqueous10% sodium hydroxide solution. The extract was neutralized with gaseouscarbon dioxide, and a solid was collected by filtration. The solid wasair dried to yield 11.0 g of1-(4-chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;mp 193°-195° C.

The nmr spectrum was consistent with the proposed structure.

Step E:1-(4-Chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one

A stirred mixture of 10.0 g (0.039 mole) of1-(4-chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one,10.0 g (0.031 mole) of tetrabutylammonium bromide and 10.0 grams (0.25mole) of sodium hydroxide in 250 mL of cyclohexane was warmed to 60° C.Chlorodifluoromethane (10.0 g, 0.12 mole) was bubbled into the reactionmixture. After complete addition the reaction mixture was warmed toreflux where it stirred for one hour. The hot solution was decanted froma pot residue and cooled to ambient temperature. Methylene chloride wasadded to the cooled mixture to dissolve a solid precipitate. The mixturewas washed with 10% hydrochloric acid then with an aqueous 10% sodiumhydroxide solution. The organic layer was dried with anhydrous magnesiumsulfate and filtered. The filtrate was concentrated under reducedpressure to yield 5.0 g of1-(4-chloro-2-fluoro-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;mp 86°-88° C.

The nmr spectrum was consistent with the proposed structure.

Step F:1-(4-Chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

A stirred mixture of 4.6 g (0.015 mole) of1-(4-chloro-2-fluoro-5-methoxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-onein 200 mL of methylene chloride was cooled to 10° C. and a solution of11.2 g (0.045) mole of boron tribromide in 45 mL of methylene chloridewas added. Upon complete addition the reaction mixture was stirred forfour hours as it warmed to ambient temperature. After this time 100 mLof water was added, and stirring was continued for an additional 18hours. The organic layer was separated, dried with anhydrous magnesiumsulfate, and filtered. The filtrate was concentrated under reducedpressure to yield 4.4 g of1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;mp 147°-152° C.

The nmr spectrum was consistent with the proposed structure.

Step G: Methyl2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionate

To a stirred mixture of 1.5 g (0.0051 mole) of1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneand 0.12 g (0.0051 mole) of sodium hydride in 50 mL ofN,N-dimethylformamide was added 0.85 g (0.0051 mole) of methyl2-bromopropionate. After complete addition the reaction mixture washeated at reflux for two hours, then cooled to room temperature andstirred for approximately 18 hours. The solvent was removed byevaporation under reduced pressure leaving a residue. This residue waspartitioned between diethyl ether and water. The organic phase waswashed with an aqueous 10% sodium hydroxide solution. The organic phasewas dried over anhydrous magnesium sulfate and filtered. The filtratewas evaporated under reduced pressure to yield 1.5 g of methyl2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionateas an oil, Compound 3.

The nmr spectrum was consistent with the proposed structure.

The following compounds were also prepared by the process of Example 2,Step G, from1-(2,4-dichloro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one;or compound A2 and one of the following reagents:

    ______________________________________                                        Compound      Reagent                                                         ______________________________________                                        1             methyl bromoacetate                                             2             methyl 2-bromopropionate                                        5             ethyl 2-bromopropionate                                         6             ethyl 2-bromopropionate                                         18            ethyl 4-bromopropionate                                         20            ethyl 2-bromoisobutyrate                                        B21           N,N--diethyl-2-chloroacetamide                                  C8            N,N--diethyl-2-chloroacetamide                                  ______________________________________                                    

Step H:2-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid

A stirred mixture of 1.3 g (0.0034 mole) ofmethyl-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionateand 1.0 g (0.018 mole) of potassium hydroxide in 15 mL of ethanol and 15mL of water was heated at reflux for three hours. The mixture wasallowed to cool to room temperature and stand for two days. The solventwas evaporated from the mixture leaving a solid. This solid wasdissolved in water, and the solution was made acidic with concentratedhydrochloric acid. This solution was extracted with methylene chloride.The extract was dried over anhydrous magnesium sulfate and filtered.Evaporation of the solvent from the filtrate left 0.85 g of2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid as a solid (mp 50°-55° C.), Compound A2.

Compound A1 was also prepared by the method of Example 2, Step H, fromCompound 2.

Analysis Calc'd for C₁₆ H₁₅ N₃ Cl₂ F₂ O₄ : C 45.52; H 3.58; N 9.95;Found: C 45.24; H 3.76; N 9.87.

EXAMPLE 3N-methylsulfonyl-2-[2,4-Dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide

Step A:2-[2,4-Dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]-propionylchloride

A stirred mixture of 2.9 g (0.0075 mole) of2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H,1,2,4-triazol-1-yl)phenoxy]propionic acid (Compound A-1) in 5 mL ofthionyl chloride was heated at reflux for 1.5 hours. The mixture wascooled, and the excess thionyl chloride was removed by evaporation underreduced pressure, leaving 3.1 g of product as an oil.

Step B:N-Methylsulfonyl-2-[2,4-dichloro-5-(4-difluoro-methyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide

A mixture of 0.56 g of the oil from Step A and 0.56 g (0.0059 mole) ofmethanesulfonamide was heated at 80° C. for 3.5 hours. The mixture wascooled and diluted with water, forming a gummy precipitae. The water wasdecanted, and the residue was partitioned between water and methylenechloride. The organic phase was washed with three 100 ml portions ofwater, dried over anhydrous magnesium sulfate, and filtered. Thefiltrate was evaporated under reduced pressure to leave a tan solidwhich was dissolved in 30 mL of 1N sodium hydroxide and 50 mL of water.The basic mixture was filtered, and the filtrate was made acidic withconcentrated hydrochloric acid. A precipitate formed and was collectedby filtration. The filter cake was washed with water and dried to yield0.34 g ofN-methylsulfonyl-2-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide(mp 185°-188° C.), Compound C3.

The nmr spectrum was consistent with the proposed structure.

Analysis Calc'd for C₁₄ H₁₄ Cl₂ F₂ N₄ O₅ S: C 36.61; H 3.07; N 12.20.Found: C 36.79; H 3.01; N 12.41.

Compounds C4, C5 and C6 were prepared by the process described inExample 3 using trifluoromethanesulfonamide, ammonia and methylamiderespectively in Step B. Compounds C2 and C18 were prepared by the methodof Example 3 from Compound A2, using methylamine and methanesulfonamiderespectively in Step B.

EXAMPLE 4N-(4-Methylphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide

A stirred mixture of 0.78 g (0.0021 mole) of2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid, 0.42 g (0.0021 mole) of p-toluenesulfonyl isocyanate and 0.05 g(0.0004 mole) of 4-dimethylaminopyridine in 50 mL of toluene was heatedat reflux for approximately 18 hours. The mixture was allowed to cool toroom temperature and was stirred for 24 hours. The solvent was removedby evaporation at reduced pressure to leave a residue. This residue waspurified by column chromatography on silica gel, eluting withtoluene:ethyl acetate (1:1). The appropriate fractions were combined andevaporated under reduced pressure to yield 0.7 g ofN-(4-methylphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamideas a solid, Compound C10.

The nmr spectrum was consistent with the proposed structure.

Compound C25 was prepared by the method of Example 4 using2-chlorobenzenesulfonyl isocyanate.

EXAMPLE 52-[2-Chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid, sodium salt.

A mixture of 1.0 g (0.0027 mole) of2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid and 0.07 g (0.0027 mole) of sodium hydride in 30 mL oftetrahydrofuran was stirred at room temperature for approximately 18hours. The solvent was removed by evaporation to yield 0.9 g of2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionicacid, sodium salt as a solid, Compound A4.

Compounds C19 and C20 were prepared by the method of Example 5 fromcompounds C18 and C10 respectively. Compound A6 was prepared by a methodanalogous to that of Example 5 from Compound A2, substitutingisopropylamine for sodium hydride.

The following compounds were prepared by the process of S.Chandrasekaran et al., Synthetic Communications, 12(9), 727-731 (1982)from Compound A2 and the following reagents.

    ______________________________________                                        Compound   Reagent                                                            ______________________________________                                        B8         tetrahydrofurfuryl alcohol                                         B9         methyl hydroxyacetate                                              B10        2-methyl-3,3,4,4-tetrafluoro-2-butanol                             B12        furfuryl alcohol                                                   B13        N,N--dimethylethanolamine                                          B14        3-hydroxytetrahydrofuran                                           B15        phenol                                                             B17        ethanethiol                                                        B18        ethyl 2-mercaptoacetate                                            B30        trifluoroethanol                                                   B31        acetone cyanohydrin                                                B32        benzyl alcohol                                                     B33        2-propanethiol                                                     C11        O,N--dimethylhydroxylamine hydrochloride                           C12        (2-propynyl)amine                                                  C13        aniline                                                            C14        dimethylamine                                                      C15        diethylamine                                                       C16        ethylamine hydrochloride                                           C17        glycine methyl ester hydrochloride                                 C22        2-amino-2-methylpropionitrile                                      C23        N--methylaniline                                                   ______________________________________                                    

Characterizing properties of some of the compounds of the invention aregiven in Table 2 below.

EXAMPLE 6N-(2,5-dimethoxyphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide

Step A: 2,5-Dimethoxyphenylsulfonamide

To a stirred solution of 15.0 g (0.063 mole) of2,5-dimethoxybenzenesulfonyl chloride in 150 mL of tetrahydrofuran wasadded dropwise 80 mL of ammonia (28% aqueous solution). After completeaddition the mixture was allowed to stir for 1.75 hours at roomtemperature. Upon standing the mixture separated into two phases. Theorganic phase was removed from the aqueous phase and was evaporatedunder reduced pressure to leave a solid residue. This residue wasrecrystallized from hot water (125 mL) and ethanol (40 mL) to yield 13.1g of 2,5-dimethoxyphenylsulfonamide (mp 146.5-148.5).

The nmr spectrum was consistent with the proposed structure.

Step B: N-(2,5-Dimethoxyphenylsulfonyl)-2-bromopropionamide

A stirred mixture of 7.0 g (0.032 mole) of2,5-dimethoxyphenylsulfonamide in 10 mL of 2-bromopropionyl chloride washeated at reflux for 40 minutes then allowed to cool to roomtemperature. The resultant solution was poured into petroleum ether.Crystals formed after scratching the sides of the flask and werecollected by filtration. The filter cake was washed four times withfresh petroleum ether to yield 10.3 g ofN-(2,5-dimethoxyphenylsulfonyl)-2-bromopropionamide (mp 116°-118° C.).

The nmr spectrum was consistent with the proposed structure.

Step C:N-(2.5-Dimethoxyphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide

To a stirred solution of 0.75 g (0.0026 mole) of1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneand 0.89 g (0.0026 mole) ofN-(2,5-dimethoxyphenylsulfonyl)-2-bromopropionamide in 50 mL of acetonewas added 1.04 g (0.0026 mole) of potassium carbonate. After completeaddition the mixture was heated at 45° C. for two days. The resultantmixture was cooled and the solvent was removed by evaporation underreduced pressure to leave a residue. This residue was dissolved in 100mL of water. The aqueous solution was acidified by the dropwise additionof concentrated hydrochloric acid producing a precipitate. Theprecipitate was collected by filtration. The filter cake was washed withwater and then dried under reduced pressure to leave 1.23 ofN-(2,5-dimethoxyphenylsulfonyl)-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide(mp 168°-172° C.) Compound C90.

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 71-(4-Chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-oneas an intermediate

Step A: N'-(4-Chloro-2-fluoro-5-methoxyphenyl)acetamidrazone

A stirred mixture of 1.91 g (0.01 mole) of4-chloro-2-fluoro-5-methoxyphenylhydrazine and 1.97 g (0.01 mole) of3-(1-iminoethylmercapto)-1-propanesulfonic acid, inner salt, (preparedby the method of Reid et al, Ann. Chem. 676, 114 (1964)) in 50 mL ofanhydrous ethanol was heated at reflux for 1.25 hours. The mixture wascooled and evaporated under reduced pressure to leave 3.96 g of aresidue. A portion of this residue, 3.33 g, was dissolved in 50 mL ofwater. The resultant cloudy solution was filtered through a pad ofcelite and the filtrate was extracted with methylene chloride. Theclarified aqueous solution was basified with approximately 8 mL of anaqueous 10% sodium hydroxide solution. An oil precipitated from thebasic mixture and slowly solidified. This solid was collected byfiltration. The filter cake was washed with water to yield 1.31 g ofN'-(4-chloro-2-fluoro-5-methoxyphenyl)acetamidrazone (mp 106°-107° C.).

The nmr analysis was consistent with the proposed structure.

Analysis calc'd for C₉ H₁₁ ClFN₃ O: C 46.66, H 4.79, N 18.14. Found: C46.10, H 4.81, N 17.70.

Step B:1-(4-Chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one

A solution of 1.71 g (0.0086 mole) of trichloromethyl chloroformate in 5mL of toluene was added dropwise to a stirred solution of 1.0 g (0.0043mole) of N'-(4-chloro-2-fluoro-5-methoxyphenyl)acetamidrazone in 50 mLof toluene. After complete addition the mixture was stirred at roomtemperature for five minutes then was heated slowly until a slow refluxwas obtained. Reflux was maintained for approximately 15 minutes. Themixture was cooled and evaporated under reduced pressure to leave 1.22 gof a solid. Approximately 1.0 g of this solid was dissolved in 100 mL ofmethylene chloride. The resultant solution was filtered and the filtratewas extracted with three 25 mL portions of an aqueous 10% sodiumhydroxide solution followed by three 25 mL portions of 1N sodiumhydroxide. Each set of three similar extracts were combined and washedwith methylene chloride. Both of the washed extracts were acidified withconcentrated hydrochloric acid producing a precipitate from each. Thesolids were collected by filtration to provide 0.3 g and 0.12 g, fromthe 10% and 1N base solutions respectively, of1-(4-chloro-2-fluoro-5-methoxyphenyl)-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one(mp 209°-211° C.).

The nmr spectrum was consistent with the proposed structure.

EXAMPLE 81-(2,4-Dichloro-5-hydroxyphenyl)-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-oneas an intermediate

Step A:N'-[2,4-Dichloro-5-(1-methylethoxy)phenyl]chlorodifluoroacetamidrazone

A stirred solution of 9.4 g (0.04 mole) of2,4-dichloro-5-(1-methylethoxy)phenylhydrazine in 350 mL of absolutemethanol was cooled to 0°. Gaseous chlorodifluoroacetonitrile (8.0 g,0.07 mole) was added to the mixture. After complete addition the mixturewas allowed to warm to room temperature and stir for 3.5 hours. Thestirring was stopped and the mixture stood at room temperature for twodays. The solvent was evaporated from the mixture under reduced pressureto leave 13.86 g ofN'-[2,4-dichloro-5-(1-methylethoxy)phenyl]chlorodifluoroacetamidrazoneas an oily residue.

Step B:1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one

In a manner similar to Example 8, Step B, the reaction of 13.86 g of theoily residue from Step A plus 2.7 g of similar material prepared in aseparate experiment and 19.87 g (0.1 mole) of trichloromethylchloroformate in 600 mL of toluene produced 5.4 g of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one(mp 115°-119° C.).

The nmr spectrum was consistent with the proposed structure.

Step C:1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one

Reaction of 4.0 g (0.011 mole) of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-1,2,4-triazol-5(1H)-one,4.26 g (0.03 mole) of methyl iodide, and 2.07 g (0.015 mole) ofpotassium carbonate in 40 mL of acetone provided 3.74 g of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-oneas a solid. Recrystallization of a small portion of this solid fromethanol and water provided a pale yellow solid, mp 69°-72° C.

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for C₁₃ H₁₂ Cl₃ F₂ N₃ O₂ : C 40.39, H 3.13, N 10.87.Found: C 40.92, H 3.28, N 10.96.

Step D:1-(2,4-Dichloro-5-hydroxyphenyl)-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-one

Hydrolysis of 2.6 g (0.0067 mole) of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-onein 10 mL of concentrated sulfuric acid produced 2.17 g of1-(2,4-dichloro-5-hydroxyphenyl)-3-chlorodifluoromethyl-4,5-dihydro-4-methyl-1,2,4-triazol-5(1H)-oneas a solid (mp 146°-148° C.).

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for C₁₀ H₆ Cl₃ F₂ N₃ O₂ : C 34.86, H 1.76, N 12.20.Found: C 35.30, H 1.59, N 12.25.

EXAMPLE 9 Synthesis ofN-(2,3-dihydro-2,2-dimethylbenzofuran-7-yl)sulfonyl-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide

Step A: Synthesis of 7-chlorosulfonyl-2,3-dihydro-2,2-dimethylbenzofuran

Stirred glacial acetic acid, 52 ml, was cooled in an ice-salt bath andgaseous sulfur dioxide was bubbled in during a one-hour period. Afterthis time a mixture of 3.8 grams (0.027 mole) of copper (II) chloride in26 ml of toluene, followed by 5.1 grams (0.054 mole) of magnesiumchloride, were added.

In a separate reaction vessel, a stirred slurry of 11.2 grams (0.068mole) of 7-amino-2,3-dihydro-2,2-dimethylbenzofuran and 15 ml ofconcentrated hydrochloric acid was cooled in an ice-salt bath and anaqueous solution (8 ml) saturated with sodium nitrite (6.1 grams; 0.077mole) was added slowly.

The contents of both reaction vessels were quickly warmed to 30° C. and,with stirring, the diazonium salt-hydrochloric acid mixture wascarefully poured into the sulfur dioxide-acetic acid mixture. Uponcompletion of addition the reaction mixture was stirred for one hour.Water, 177 ml, was added and the reaction mixture stirred for anadditional one hour. The reaction mixture was extracted with two 100 mlportions of toluene. The combined extracts were washed in successionwith water, an aqueous solution of 10% sodium hydroxide, and finallywith water. The organic layer was dried with magnesium sulfate andfiltered. The filtrate was concentrated under reduced pressure to yield11.0 grams of 7-chlorosulfonyl-2,3-dihydro-2,2-dimethylbenzofuran; B.p.130°-150° C./1.5 mm.

Step B: Synthesis of 7-aminosulfonyl-2,3-dihydro-2,2-dimethylbenzofuran

A solution of 0.5 gram (0.002 mole) of7-chlorosulfonyl-2,3-dihydro-2,2-dimethylbenzofuran and 4 ml oftetrahydrofuran was stirred and 2 ml of an aqueous solution of 29%ammonium hydroxide was added. The reaction mixture stirred for one hour,then was concentrated under reduced pressure to a residue. The residuewas triturated with water and filtered to collect, when dried, 0.41grams of 7-aminosulfonyl-2,3-dihydro-2,2-dimethylbenzofuran; m.p.160.5°-162.5° C.

Step C: Synthesis ofN-(2,3-dihydro-2,2-dimethylbenzofuran-7-yl)sulfonyl-2-bromopropionamide

A stirred slurry of 0.39 gram (0.0017 mole) of7-aminosulfonyl-2,3-dihydro-2,2-dimethylbenzofuran and 1 ml of2-bromopropionyl chloride was heated at 96° for 35 minutes, then atreflux for 30 minutes. The reaction mixture was cooled to ambienttemperature and washed repeatedly with petroleum ether to remove excessacid chloride. The residue was 0.53 gram ofN-(2,3-dihydro-2,2-dimethylbenzofuran-7-yl)sulfonyl-2-bromopropionamide;m.p. 224°-226° C.

The NMR spectrum was consistent with the proposed structure.

Step D: Synthesis ofN-(2,3-dihydro-2,2-dimethylbenzofuran-7-yl)sulfonyl-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide.

A stirred mixture of 0.2 gram (0.0007 mole) of1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one,0.3 gram (0.0007 mole) ofN-(2,3-dihydro-2,2-dimethylbenzofuran-7-yl)sulfonyl-2-bromopropionamide,0.3 gram (0.002 mole) of potassium carbonate in 20 ml of acetone washeated under reflux for 18 hours. The reaction mixture was cooled andconcentrated under reduced pressure to a residue. The residue wasdissolved in 100 ml of water and the solution acidified by the dropwiseaddition of concentrated hydrochloric acid. The resultant precipitatewas collected by filtration, washed with water, and dried to yieldN-(2,3-dihydro-2,2-dimethylbenzofuran-7-yl)sulfonyl-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide;m.p. 198°-201° C.

The NMR spectrum was consistent with the proposed structure.

Analysis calculated for C₂₃ H₂₂ ClF₃ N₄ O₆ S: C 48.05; H 3.86; N 9.74.Found: C 47.11; H 3.89; N 9.34.

EXAMPLE 10N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)sulfonyl-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamide

Step A: 5-Chlorosulfonyl-2,3-dihydro-2,2-dimethylbenzofuran

To a stirred solution of 22.2 g (0.15 mole) of2,3-dihydro-2,2-dimethylbenzofuran in 190 mL of chloroform was addeddropwise 20 mL (0.3 mole) of chlorosulfonic acid. After completeaddition, the reaction mixture was stirred at room temperature for twohours. The reaction mixture was poured into a separatory funnel with icewater and shaken. The organic layer was separated from the aqueous phaseand dried over anhydrous magnesium sulfate. The dried organic phase wasfiltered and the filtrate was evaporated under reduced pressure to leave14.5 g of 5-chlorosulfonyl-2,3-dihydro-2,2-dimethylbenzofuran as a solid(mp 75°-77° C.).

The nmr spectrum was consistent with the proposed structure.

Step B: 5-Aminosulfonyl-2,3-dihydro-2,2-dimethylbenzofuran

In a manner similar to Step B of Example 9, the reaction of 9.0 g (0.036mole) of 5-chlorosulfonyl-2,3-dihydro-2,2-dimethylbenzofuran with 60 mLof an aqueous 29% ammonium hydroxide solution in 70 mL oftetrahydrofuran produced 8.0 g of5-aminosulfonyl-2,3-dihydro-2,2-dimethylbenzofuran as a solid (mp157°-160° C.).

Analysis calc'd for C₁₀ H₁₃ NO₃ S: C 52.85; H 5.76; N 6.16; Found: C52.82; H 5.49; N 5.87.

Step C:N-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)sulfonyl-2-bromopropionamide

In a manner similar to Step C of Example 9, the reaction of 4.0 g (0.017mole) of 5-aminosulfonyl-2,3-dihydro-2,2-dimethylbenzofuran with 7.0 mL(0.069 mole) of 2-bromopropionyl chloride produced 5.4 g ofN-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)sulfonyl-2-bromopropionamideas a solid (mp 125°-128° C.).

Analysis calc'd for C₁₃ H₁₆ BrNO₄ S: C 43.10; H 4.45; N 3.87; Found: C43.27; H 4.18; N 3.57.

Step D:N-(2,3-Dihydro-2,2-dimethylbenzofuran-5-yl)sulfonyl-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)-phenoxy]propionamide

In a manner similar to Step D of Example 9, the reaction of 0.5 g(0.0017 mole) of1-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-onewith 0.7 g (0.0051 mole) of potassium carbonate and 0.62 g (0.0017 mole)ofN-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)sulfonyl-2-bromopropionamidein 35 mL of acetone produced 0.89 g ofN-(2,3-dihydro-2,2-dimethylbenzofuran-5-yl)sulfonyl-2-[2-chloro-4-fluoro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenoxy]propionamideas a solid.

The nmr spectrum was consistent with the proposed structure.

Analysis calc'd for C₂₃ H₂₂ ClF₃ N₄ O₆ S: C 48.05; H 3.86; N 9.74.Found: C 47.21; H 3.95; N 9.31.

HERBICIDAL ACTIVITY

The plant test species used in demonstrating the herbicidal activity ofcompounds of this invention include cotton (Gossypium hirsutum var.Stoneville), soybean (Glycine max var. Williams), field corn (Zea maysvar. Agway 595S), wheat (Triticum aestivium var. Prodax), rice (Oryzasativa), field bindweed (Convolvulus arvensis), morningglory (Ipomealacunosa or Ipomea hederacea, velvetleaf (Abutilon theophrasti),barnyardgrass (Echinochloa crus galli), green foxtail (Setaria viridis),and johnsongrass (Sorghum halepense), yellow nutsedge (Cyperusesculentus).

Seeds or tubers of the plant test species were planted in furrows insteam sterilized sandy loam soil contained in disposable fiber flats. Atopping soil of equal portions of sand and sandy loam soil was placeduniformly on top of each flat to a depth of approximately 0.5 cm.

The flats for the preemergence test were watered, then drenched with theappropriate amount of a solution of the test compound in a mixture ofacetone and water containing a small amount (up to 0.5% v/v) of sorbitanmonolaurate emulsifier/solubilizer. The concentration of the testcompound in solution was varied to give a range of application rates,generally 8.0 kg/ha and submultiples thereof. The flats were placed in agreenhouse and watered regularly at the soil surface for 21 days atwhich time phytotoxicity data were recorded.

The flats for the postemergence test were placed in a greenhouse andwatered for 8-10 days, then the foilage of the emerged test plants wassprayed with a solution of the test compound in acetone-water containingup to 0.5% sorbitan monolaurate. After spraying, the foilage was keptdry for 24 hours, then watered regularly for 21 days, and phytotoxicitydata recorded.

For testing the effectiveness with paddy rice, plastic flats (35.5cm×6.4 cm×12.7 cm) were lined with plastic film and filled to a depth ofabout 3.0 cm with steam-sterilized sandy loam soil. The soil was leveledand seeds of rice (Oryza sativa var. Mars or Labelle) and flatsedge rice(Cyperus iria), a weed, were planted and topped with about 0.5 cm ofsandy loam soil. The flat was placed in the greenhouse and watered for 7to 8 days. Hemp Sesbania (Sesbania exaltata), barnyardgrass (EchinochloaCrus-galli), and green sprangletop (Leptochloa imbricata) were plantedin the remaining space in the flat. The flats were again placed in thegreenhouse and watered for another seven or eight days so that all theseeds sprouted. The flats were then drenched with water to a level of 2to 3 cm above the soil. Directly after their drenching the candidateherbicides were applied as aqueous-acetone solutions at a range of ratesequivalent to 0.5 kg/ha and submultiples thereof, i.e. 0.25 kg/ha, 0.125kg/ha, and so on. The appropriate amount of test solution was pipettedinto the water layer above the soil, distributing the solution evenly.After application of the test solution the drenched flats were placed inthe greenhouse and watered regularly to keep the soil covered withwater. After 14 days phytotoxicity data were recorded and expressed aspercent control as compared to a flat which had not been treated withherbicide. The temperature of the greenhouse was about 30° C.

Phytotoxicity data were taken either as percent kill or percent control.Percent control was determined by a method similar to the 0 to 100rating system disclosed in "Research Methods in Weed Science," 2nd ed.,B. Truelove, Ed.; Southern Weed Science Society; Auburn University,Auburn, Ala., 1977. The present rating system is as follows:

HERBICIDE RATING SYSTEM

    ______________________________________                                        Rating Description                                                            Percent                                                                              of Main   Crop          Weed                                           Control                                                                              Categories                                                                              Description   Description                                    ______________________________________                                         0     No effect No crop       No Weed                                                         reduction     control                                                         or injury                                                    10     Slight    Slight dis-   Very poor weed                                        effect    coloration    control                                                         or stunting                                                  20               Some dis-     Poor weed                                                       coloration,   control                                                         stunting or                                                                   stand loss                                                   30               Crop injury   Poor to defi-                                                   more pronounced                                                                             cient weed                                                      but not lasting                                                                             control                                        40     Moderate  Moderate injury,                                                                            Deficient weed                                        effect    crop usually  control                                                         recovers                                                     50               Crop injury   Deficient to                                                    more lasting, moderate weed                                                   recovery      control                                        60               Lasting crop  Moderate weed                                                   injury no     control                                                         recovery                                                     70     Severe    Heavy injury and                                                                            Control some-                                                   stand loss    what less than                                                                satisfactory                                   80               Crop nearly de-                                                                             Satisfactory                                                    stroyed a few to good weed                                                    survivors     control                                        90               Only occasional                                                                             Very good to                                                    live plants left                                                                            excellent                                                                     control                                        100    Complete  Complete crop Complete weed                                         effect    destruction   destruction                                    ______________________________________                                    

Herbicidal data at selected application rates are given for variouscompounds of the invention in the tables below. The test compounds areidentified in the tables of herbicidal data below by numbers whichcorrespond to those used above.

In the Tables of herbicidal data below:

"kg/ha" is kilograms per hectare,

"% K" is percent kill, and

"% C" is percent control.

For herbicidal application, the active compounds as above defined areformulated into herbicidal compositions by admixture in herbicidallyeffective amounts with adjuvants and carriers normally employed in theart for facilitating the dispersion of active ingredients for theparticular utility desired, recognizing the fact that the formulationand mode of application of a toxicant may affect the activity of thematerial in a given application. Thus, for agricultural use the presentherbicidal compounds may be formulated as granules of relatively largeparticle size, water-soluble or water-dispersible granules, as powderydusts, as wettable powders, as emulsifiable concentrates, as solutionsor as any of several other known types of formulations, depending on thedesired mode of application.

For preemergence application these herbicidal compositions are usuallyapplied either as sprays, dusts, or granules to the areas in whichsuppression of vegetation is desired. For postemergence control ofestablished plant growth, sprays or dusts are most commonly used. Theseformulations may contain as little as 0.5% to as much as 95% or more byweight of active ingredient.

Dusts are free flowing admixtures of the active ingredient with finelydivided solids such as talc, natural clays, kieselguhr, flours such aswalnut shell and cottonseed flours, and other organic and inorganicsolids which act as dispersants and carriers for the toxicant; thesefinely divided solids have an average particle size of less than about50 microns. A typical dust formulation useful herein is one containing1.0 part of the herbicidal compound and 99.0 parts of talc.

Wettable powders, also useful formulations for both pre- andpostemergence herbicides, are in the form of finely divided particleswhich disperse readily in water or other dispersant. The wettable powderis ultimately applied to the soil either as a dry dust or as an emulsionin water or other liquid. Typical carriers for wettable powders includeFuller's earth, kaolin clays, silicas, and other highly absorbent,readily wet inorganic diluents. Wettable powders normally are preparedto contain about 5-80% of active ingredient, depending on the absorbencyof the carrier, and usually also contain a small amount of a wetting,dispersing or emulsifying agent to facilitate dispersion. For example, auseful wettable powder formulation contains 80.8 parts of the herbicidalcompound, 17.9 parts of Palmetto clay, and 1.0 part of sodiumlignosulfonate and 0.3 part of sulfonated aliphatic polyester as wettingagents. Frequently, additional wetting agent and/or oil will be added tothe tank-mix for postemergence application to facilitate dispersion onthe foliage and absorption by the plant.

Other useful formulations for herbicidal applications are emulsifiableconcentrates. Emulsifiable concentrates are homogeneous liquid or pastecompositions dispersible in water or other dispersant, and may consistentirely of the herbicidal compound and a liquid or solid emulsifyingagent, or may also contain a liquid carrier, such as xylene, heavyaromatic naphthas, isophorone, or other non-volatile organic solvent.For herbicidal application these concentrates are dispersed in water orother liquid carrier, and normally applied as a spray to the area to betreated. The percentage by weight of the essential active ingredient mayvary according to the manner in which the composition is to be applied,but in general comprises 0.5 to 95% of active ingredient by weight ofthe herbicidal composition.

Typical wetting, dispersing or emulsifying agents used in agriculturalformulations include, for example, the alkyl and alkylaryl sulfonatesand sulfates and their sodium salts; polyhydric alcohols; and othertypes of surface active agents, many of which are available in commerce.The surface active agent, when used, normally comprises 1% to 15% byweight of the herbicidal composition.

Other useful formulations for herbicidal applications include simplesolutions of the active ingredient in a dispersant in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene or other organic solvents. Granularformulations, wherein the toxicant is carried on relatively coarseparticles, are of particular utility for aerial distribution or forpenetration of cover crop canopy. Pressurized sprays, typically aerosolswherein the active ingredient is dispersed in finely divided form as aresult of vaporization of a low boiling dispersant solvent carrier, suchas the Freons, may also be used. Water-soluble or water-dispersiblegranules are also useful formulations for herbicidal application of thepresent compounds. Such granular formulations are free-flowing,non-dusty, and readily water-soluble or water-miscible. The soluble ordispersible granular formulations described in U.S. Pat. No. 3,920,442,incorporated herein by reference, are useful herein with the presentherbicidal compounds.

The active herbicidal compounds of this invention may be formulatedand/or applied with insecticides, fungicides, nematicides, plant growthregulators, fertilizers, or other agricultural chemicals and may be usedas effective soil sterilants as well as selective herbicides inagriculture. In applying an active compound of this invention, whetherformulated alone or with other agricultural chemicals, an effectiveamount and concentration of the active compound is of course employed;the amount may be as low as, for example, 7 g/ha or lower; for instanceit may be in the range of about 4 to 250 g/ha such as 7 or 15 to 65g/ha.

The active herbicidal compounds of this invention may be used incombination with other herbicides, e.g. they may be mixed with, say, anequal or larger amount of a known herbicide such as chloroacetanilideherbicides such as2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide (alachlor),2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide(metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)glycine(diethatyl-ethyl); benzothiadiazinone herbicides such as3-(1-methylethyl)-(1H)-2,1,3-benzothiadiazin-4-(3-H)-one-2,2-dioxide(bentazon); triazine herbicides such as6-chloro-N-ethyl-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine(atrazine), and2-[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]-amino-2-methylpropanenitrile(cyanazine); dinitrolaniline herbicides such as2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzeneamine (trifluralin);and aryl urea herbicides such asN'-(3,4-dichlorophenyl)-N,N-dimethylurea (diuron) andN,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (fluometuron).

It is apparent that various modifications may be made in the formulationand application of the compounds of this invention, without departingfrom the inventive concepts herein, as defined in the following claims.

                                      TABLE 1                                     __________________________________________________________________________     ##STR15##                                                                    Cmpd.                                                                         No. X  Y         R.sup.1                                                                             R.sup.2 R.sup.3                                                                            R.sup.6           R.sup.7                 __________________________________________________________________________    C1  Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                           H                 H                       C2  F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.3          H                       C3  Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 CH.sub.3 H                       C4  Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 CF.sub.3 H                       C5  Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       H                 H                       C6  Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.3          H                       C7  F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                           H                 H                       C8  F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub. 2                                                                          C.sub.2 H.sub.5   C.sub.2 H.sub.5         C9  F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH(CH.sub.3)C.sub.2 H.sub.5                                                                     H                       C10 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR16##        H                       C11 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       OCH.sub.3         CH.sub.3                C12 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.2 CCH      H                       C13 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR17##        H                       C14 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.3          CH.sub.3                C15 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       C.sub.2 H.sub.5   C.sub.2 H.sub.5         C16 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       C.sub.2 H.sub.5   H                       C17 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.2 CO.sub.2 CH.sub.3                                                                      H                       C18 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 CH.sub.3 H                       C19 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 CH.sub.3 Na                      C20 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR18##        Na                      C21 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       C(CH.sub.3).sub.2 CCH                                                                           H                       C22 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       C(CH.sub.3).sub.2 CN                                                                            H                       C23 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR19##        CH.sub.3                C24 Cl Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH.sub.2                                                                           H                 H                       C25 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR20##        H                       C26 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       H                 H                       C27 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 CF.sub.3 H                       C28 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 CF.sub.3 Na                      C29 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR21##        H                       C30 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 CH.sub.3 CH.sub.3                C31 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR22##        CH.sub.3                C32 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR23##        H                       C33 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                           SO.sub.2 CH.sub.3 H                       C34 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            ##STR24##        H                       C35 F  CH.sub.3  CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       NHCH.sub.3        H                       C36 F  CH.sub.3  CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 CH.sub.3 H                       C37 F  CH.sub.3  CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                           SO.sub.2 CH.sub.3 H                       C38 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2       C39 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2      C40 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub. 3)                                                                      SO.sub.2 N(CH.sub.3).sub.2                                                                      H                       C41 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 NHCH(CH.sub.3).sub.2                                                                   H                       C42 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR25##        H                       C43 F  Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        ##STR26##        H                       C44 F  Cl        CF.sub.2 Cl                                                                         CH.sub.3                                                                              CH(CH.sub.3)                                                                       H                 CH.sub.3                C45 F  CH.sub.3  CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                       SO.sub.2 CH.sub.3 H                       C46 F  CH.sub.2 SCH.sub.3                                                                      CHF.sub.2                                                                           CH.sub.3                                                                              CH.sub.2                                                                           CH.sub.3          CH.sub.3                C47 F  Cl        CHF.sub.2                                                                           CH.sub.2 CN                                                                           CH(CH.sub.3)                                                                       H                 H                       C48 F  Cl        CHF.sub.2                                                                           CH.sub.2 SCN                                                                          CH(CH.sub.3)                                                                       H                 CH(CH.sub.3).sub.2      C49 F  Cl        CF.sub.3                                                                            CH.sub.2 OCH.sub.3                                                                    CH.sub.2                                                                           CH.sub.2 CHCH.sub.2                                                                             H                       C50 F  Cl        CF.sub.3                                                                            CH.sub.2 CHCH.sub.2                                                                   CH(CH.sub.3)                                                                        ##STR27##        H                       C51 F  Cl        CHF.sub.2                                                                           CHF.sub.2                                                                             CH(CH.sub. 3)                                                                      H                 H                       C52 Cl Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH.sub.2                                                                            ##STR28##        H                       C53 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.2 CH.sub.2 OCH.sub.3                                                                     H                       C54 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR29##        H                       C55 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                           SO.sub.2 CH.sub.2 CHCH.sub.2                                                                    H                       C56 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                           SO.sub.2 CH.sub.2 CHCH.sub.2                                                                    Na                      C57 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2                                           CH.sub.2                                  C58 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR30##        H                       C59 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR31##        H                       C60 Cl Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                       SO.sub.2 N(CH.sub.3).sub.2                                                                      H                       C61 F  Cl        CHF.sub.2                                                                           CHF.sub.2                                                                             CH(CH.sub.3)                                                                       H                 H                       C62 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR32##                                C63 CF.sub.3                                                                         Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       H                 H                       C64 F  Cl        CH.sub.2 CN                                                                         CHF.sub.2                                                                             CH(CH.sub.3)                                                                       H                 H                       C65 F  Cl        CH.sub.2 SCH.sub.3                                                                  CHF.sub.2                                                                             CH.sub.2                                                                           CH.sub.3          H                       C66 F  Cl        SCH.sub.3                                                                           CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.3          CH.sub.3                C67 F  Cl        Cl    CHF.sub.2                                                                             CH(CH.sub.3)                                                                       H                 H                       C68 F                                                                                 ##STR33##                                                                              CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       H                 H                       C69 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            ##STR34##        H                       C70 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            ##STR35##        H                       C71 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR36##        Na                      C72 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR37##        H                       C73 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR38##        H                       C74 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR39##        H                       C75 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR40##        H                       C76 Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR41##        H                       C77 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR42##        H                       C78 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR43##        H                       C79 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR44##        CH.sub.3                C80 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR45##        H                       C81 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR46##        H                       C82 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR47##        H                       C83 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR48##        Na                      C84 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR49##        CH.sub.3                C85 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR50##        H                       C86 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR51##                                C87 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR52##        H                       C88 F  Cl        CH.sub.3                                                                            CH.sub.3                                                                              CH(CH.sub.3)                                                                        ##STR53##        H                       C89 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR54##                                C90 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR55##        H                       C91 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR56##        Na                      C92 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR57##        Na                      C93 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR58##        H                       C94 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR59##        H                       C95 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR60##        H                       C96 F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2       C97 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR61##                                C98 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR62##        Na                      C99 F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR63##        H                       C100                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR64##        Na                      C101                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR65##        H                       C102                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR66##                                C103                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR67##                                C104                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR68##                                C105                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR69##        H                       C106                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR70##        Na                      C107                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR71##        H                       C108                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR72##                                C109                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR73##        H                       C110                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR74##        Na                      C111                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR75##        H                       C112                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            ##STR76##        H                       C113                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR77##        H                       C114                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR78##        Na                      C115                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR79##        H                       C116                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            ##STR80##        H                       C117                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR81##        H                       C118                                                                              Cl Cl        CClF.sub.2                                                                          CH.sub.3                                                                              CH(CH.sub.3)                                                                        ##STR82##        H                       C119                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            ##STR83##        H                       C120                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            ##STR84##        H                       C121                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            ##STR85##        Na                      C122                                                                              Cl Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        ##STR86##        H                       C123                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR87##        H                       C124                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR88##        H                       C125                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR89##        H                       C126                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR90##        H                       C127                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR91##        H                       C128                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR92##        H                       C129                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            ##STR93##        H                       C130                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            ##STR94##        Na                      C131                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR95##        H                       C132                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR96##        Na                      C133                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR97##        H                       C134                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR98##        H                       C135                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR99##        H                       C136                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR100##       H                       C137                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR101##       H                       C138                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR102##       H                       C139                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR103##       Na                      C140                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR104##       H                       C141                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR105##       H                       C142                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR106##       H                       C143                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR107##       H                       C144                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR108##       H                       C145                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR109##       H                       C146                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR110##       H                       C147                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR111##       H                       C148                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR112##       H                       C149                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR113##       H                       C150                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR114##       H                       C151                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR115##       H                       C152                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR116##       H                       C153                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR117##       H                       C154                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR118##       H                       C155                                                                              Cl Cl        CHF.sub.2                                                                           CH.sub. 3                                                                             CH(CH.sub.3)                                                                        ##STR119##       H                       C156                                                                              Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR120##       H                       C157                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 CH.sub.3 H                       C158                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub. 2 CF.sub.3                                                                              H                       C159                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 NH.sub.2 H                       C160                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR121##       H                       C161                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR122##       H                       C162                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR123##       H                       C163                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR124##       H                       C164                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR125##       H                       C165                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR126##       H                       C166                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR127##       H                       C167                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR128##       H                       C168                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR129##       H                       C169                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR130##       H                       C170                                                                              F  Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        ##STR131##       H                       C171                                                                              F  Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        ##STR132##       H                       C172                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR133##       H                       C173                                                                              F  Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        ##STR134##       H                       C174                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR135##       H                       C175                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR136##       H                       C176                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR137##       H                       C177                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR138##       H                       C178                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR139##       H                       C179                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR140##       H                       C180                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR141##       H                       C181                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR142##       H                       C182                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR143##       H                       C183                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR144##       H                       C184                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR145##       H                       C185                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       H                 H                       C186                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.3          H                       C187                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3 )                                                                      CH.sub.3          CH.sub.3                C188                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       C.sub.2 H.sub.5   H                       C189                                                                              F  Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        ##STR146##       H                       C190                                                                              F  Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                       H                 H                       C191                                                                              F  Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                       CH.sub.3          H                       C192                                                                              F  Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                       CH.sub.3          CH.sub.3                C193                                                                              F  Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                       CH.sub.3          CH.sub.3                C194                                                                              F  Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                       H                 H                       C195                                                                              F  Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                       CH.sub.3          H                       C196                                                                              Br Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                       CH.sub.3          CH.sub.3                C197                                                                              Br Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                       H                 H                       C198                                                                              Br Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                       CH.sub.3          H                       C199                                                                              Br Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       CH.sub.3          H                       C200                                                                              Br Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       H                 H                       C201                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR147##       H                       C202                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR148##       H                       C203                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR149##       H                       C204                                                                              Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR150##       H                       C205                                                                              Br Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR151##       H                       C206                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR152##       Na                      C207                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR153##       Na                      C208                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR154##       H                       C209                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR155##       H                       C210                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR156##       H                       C211                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR157##       H                       C212                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR158##       H                       C213                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR159##       H                       C214                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR160##       H                       C215                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR161##       H                       C216                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR162##       H                       C217                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR163##       H                       C218                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR164##       H                       C219                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR165##       H                       C220                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR166##       H                       C221                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR167##       H                       C222                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR168##       H                       C223                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR169##       H                       C224                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR170##       CH.sub.2 CHCH.sub.2     C225                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR171##       CH.sub.2 C CH           C226                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR172##       H                       C227                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR173##       H                       C228                                                                              F  Cl        CHF.sub.2                                                                           CH.sub. 3                                                                             CH(CH.sub.3)                                                                        ##STR174##       H                       C229                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR175##       H                       C230                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR176##       H                       C231                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR177##       H                       C232                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR178##       Na                      C233                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR179##       CH.sub.3                C234                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR180##       H                       C235                                                                              Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR181##       H                       C236                                                                              Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR182##       H                       C237                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR183##       H                       C238                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub. 3)                                                                       ##STR184##       H                       C239                                                                              Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR185##       H                       C240                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR186##       H                       C241                                                                              Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR187##       H                       C242                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR188##       H                       C243                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR189##       H                       C244                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR190##       H                       C245                                                                              F  CF.sub.3  CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR191##       H                       C246                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR192##       H                       C247                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR193##       H                       C248                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            ##STR194##       H                       C249                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR195##       H                       C250                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR196##       H                       C251                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR197##       H                       C252                                                                              F  Cl        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        ##STR198##       H                       C253                                                                              F  Cl        CClF.sub.2                                                                          CH.sub.3                                                                              CH(CH.sub.3)                                                                        ##STR199##       H                       C254                                                                              F  Cl        CF.sub.3                                                                            CH.sub.3                                                                              CH(CH.sub.3)                                                                        ##STR200##       H                       C255                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR201##       H                       C256                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR202##       H                       C257                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR203##       H                       C258                                                                              F  Br        CHF.sub.2                                                                           CH.sub.3                                                                              CH(CH.sub.3)                                                                        ##STR204##       H                       C259                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR205##       H                       C260                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR206##       H                       C261                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR207##       H                       C262                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR208##       H                       C263                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR209##       H                       C264                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR210##       H                       C265                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR211##       H                       C266                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR212##       H                       C267                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR213##       Na                      C268                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR214##       H                       C269                                                                              Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR215##       H                       C270                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR216##       Na                      C271                                                                              F  CF.sub.3  CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR217##       H                       C272                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR218##       H                       C273                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR219##       H                       C274                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR220##       H                       C275                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR221##       H                       C276                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 CH.sub.2 SO.sub.2 CH.sub.3                                                             H                       C277                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                       SO.sub.2 CH.sub.2 SCH.sub.3                                                                     H                       C278                                                                              Cl Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR222##       H                       C279                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR223##       H                       C280                                                                              F  CF.sub.3  CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR224##       H                       C281                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR225##       H                       C282                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR226##       H                       C283                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR227##       H                       C284                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR228##       H                       C285                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR229##       H                       C286                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR230##       H                       C287                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR231##       H                       C288                                                                              F  Br        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR232##       H                       C289                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR233##       H                       C290                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR234##       H                       C291                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR235##       H                       C292                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR236##       K                       C293                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR237##       (CH.sub.3).sub.2                                                              CHNH.sub.3.sup.⊕                                                          8                       C294                                                                              F  CF.sub.3  CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR238##       H                       C295                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR239##       H                       C296                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH(CH.sub.3)                                                                        ##STR240##       Na                      C297                                                                              F  Cl        CH.sub.3                                                                            CHF.sub.2                                                                             CH.sub.2                                                                            ##STR241##       H                       __________________________________________________________________________

Other representative compunds are those which are identical withcompounds C1-C95, C97-C114, C116-C122, C124-C132, C134-C140, C142-C143,C145-C147, C149-C150, C152-C156, C159, C161-C165, C168, C170, C173-C184,C186, C189-C192, C196-C225, C228-C233, C235-C241, C243-C257, C259-C272,C274-C287, and C289-297, respectively, except that X is F and Y is Br.Still other representative compounds are those which are identical withcompounds C1-C234, C246-C270, C272-C279, C281-C293 and C295-C297,respectively, except that X is F and Y is CF₃ .

                                      TABLE 2                                     __________________________________________________________________________    Identifying Properties                                                        Cmpd.                                                                             Melting                         Elemental Analysis                        No. Point (°C.)                                                                  Empirical Formula         C  H  N                                   __________________________________________________________________________    C1  209-210                                                                             C.sub.12 H.sub.10 Cl.sub.2 F.sub.2 N.sub.4 O.sub.3                            NMR δ CDCl.sub.3 /DMSO d.sub.6): 2.20(s,3H), 4.60(s,2H),                7.30(bs,3H), 7.40(5,1H,J=58Hz), 7.65(s,1H).                         C2  Oil   C.sub.14 H.sub.14 ClF.sub.3 N.sub.4 O.sub.3                                   NMR δ (CDCl.sub.3): 1.60(d,3H,J=7Hz), 2.50(s,3H),                       2.90(d,3H,J=7Hz), 4.75(q,1H,J=7Hz), 6.80(bs,1H),                              7.10(t,1H,J=58Hz), 7.20-7.45 (m,2H).                                C3  185-188                                                                             C.sub.14 H.sub.14 Cl.sub.2 F.sub.2 N.sub.4 O.sub.5 S                                                  C 36.61                                                                            3.07                                                                             12.20                                                                 F 36.79                                                                            3.01                                                                             12.41                                         NMR δ (CDCl.sub.3): 1.70(d,3H,J=7Hz), 2.50(s,3H),                       3.40(s,3H), 4.80(q,1H,J=7Hz), 7.10(s,1H),                                     7.10(t,1H,J=58Hz), 7.70(s,1H).                                      C4  Oil   C.sub.14 H.sub.11 Cl.sub.2 F.sub.5 N.sub.4 O.sub.5 S                                                  C 32.76                                                                            2.16                                                                             10.92                                                                 F 32.80                                                                            2.05                                                                             8.77                                          NMR δ (CDCl.sub.3): 1.70(d,3H,J=7Hz), 2.50(s,3H),                       4.90(q,1H,J=7Hz), 7.10(s,1H), 7.10(t,1H,J=58Hz),                              7.60(s,1H), 8.50(bs,1H).                                            C5  132-135                                                                             C.sub.13 H.sub.12 Cl.sub.2 F.sub.2 N.sub.4 O.sub.3                  C6  142-144                                                                             C.sub.14 H.sub.14 Cl.sub.2 F.sub.2 N.sub.4 O.sub.3                  C7  173-175                                                                             C.sub.12 H.sub.10 ClF.sub.3 N.sub.4 O.sub.3                         C8  105-110                                                                             C.sub.16 H.sub.18 ClF.sub.3 N.sub.4 O.sub.3                         C9  Oil   C.sub.17 H.sub.20 ClF.sub.3 N.sub.4 O.sub.3                         C10 Solid C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                                                         C 46.29                                                                            3.50                                                                             10.80                                                                 F 46.77                                                                            4.12                                                                             11.03                               C11 Oil   C.sub.15 H.sub.16 ClF.sub.3 N.sub.4 O.sub.4                                                           C 44.07                                                                            3.94                                                                             13.71                                                                 F 38.44                                                                            3.67                                                                             11.28                               C12 Solid C.sub.16 H.sub.14 ClF.sub.3 N.sub.4 O.sub.3                                                           C 47.71                                                                            3.50                                                                             13.91                                                                 F 46.03                                                                            3.60                                                                             13.91                               C13 57    C.sub.19 H.sub.16 ClF.sub.3 N.sub.4 O.sub.3                                                           C 51.77                                                                            3.66                                                                             12.71                                                                 F 50.90                                                                            4.00                                                                             11.88                               C14 Oil   C.sub.15 H.sub.16 ClF.sub.3 N.sub.4 O.sub.3                         C15 Solid C.sub.17 H.sub.20 ClF.sub.3 N.sub.4 O.sub.3                         C16 Oil   C.sub.15 H.sub.16 ClF.sub.3 N.sub.4 O.sub.3                         C17 Solid C.sub.16 H.sub.16 ClF.sub.3 N.sub.4 O.sub.5                         C18 145-150                                                                             C.sub.14 H.sub.14 ClF.sub.3 N.sub.4 O.sub.5 S                       C19 Solid C.sub.14 H.sub.14 ClF.sub.3 N.sub.4 NaO.sub.5 S                     C20 Solid C.sub.20 H.sub.17 ClF.sub.3 N.sub.4 NaO.sub.5 S                     C21 Oil   C.sub.18 H.sub.18 ClF.sub.3 N.sub.4 O.sub.3                                                           C 50.18                                                                            4.21                                                                             13.00                                                                 F 50.95                                                                            3.91                                                                             12.38                               C22 Oil   C.sub.17 H.sub.17 ClF.sub.3 N.sub.5 O.sub.3                         C23 Oil   C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.3                         C25 Solid C.sub.19 H.sub.15 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                                                  C 42.31                                                                            2.80                                                                             10.39                                                                 F 40.44                                                                            2.91                                                                             8.56                                C26 142-143                                                                             C.sub.13 H.sub.12 ClF.sub.3 N.sub.4 O.sub.3                         C32 127-134                                                                             C.sub.19 H.sub.16 ClF.sub.3 N.sub.4 O.sub.5 S                       C38 47-54 C.sub.17 H.sub.18 ClF.sub.3 N.sub.4 O.sub.3                                                           C 48.75                                                                            4.33                                                                             13.38                                                                 F 47.06                                                                            3.73                                                                             12.36                               C42 Oil   C.sub.21 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                       C43 162-166                                                                             C.sub.19 H.sub.15 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                C59 100-105                                                                             C.sub.21 H.sub.18 ClF.sub.3 N.sub.4 O.sub.7 S                                                         C 44.81                                                                            3.40                                                                             9.95                                                                  F 42.20                                                                            2.81                                                                             9.61                                C69 Solid C.sub.19 H.sub.16 ClF.sub.3 N.sub.4 O.sub.5 S                                                         C 45.20                                                                            3.19                                                                             11.10                                                                 F 44.74                                                                            3.55                                                                             10.59                               C70 208-208.5                                                                           C.sub.18 H.sub.13 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                                                  C 41.16                                                                            2.49                                                                             10.67                                                                 F 44.11                                                                            3.08                                                                             10.96                               C71 Solid C.sub.19 H.sub.14 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 SNa              C72 135-140                                                                             C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                       C73 Solid C.sub.19 H.sub.15 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                C74 110   C.sub.19 H.sub.15 ClF.sub.3 N.sub.5 O.sub.7 S                       C75 175-180                                                                             C.sub.19 H.sub.14 Cl.sub.3 F.sub.3 N.sub.4 O.sub.5 S                C76 171-173                                                                             C.sub.19 H.sub.15 Cl.sub.3 F.sub.2 N.sub.4 O.sub.5 S                C77 66-70 C.sub.19 H.sub.15 ClF.sub.4 N.sub.4 O.sub.5 S                       C78 248-253                                                                             C.sub.22 H.sub.22 ClF.sub.3 N.sub.4 O.sub.5 S                       C79 Solid C.sub.21 H.sub.20 ClF.sub.3 N.sub.4 O.sub.5 S                       C80 67-70 C.sub.20 H.sub.15 ClF.sub.6 N.sub.4 O.sub.5 S                       C81 58-62 C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.6 S                       C82 Solid C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                       C83 108-113                                                                             C.sub.20 H.sub.17 ClF.sub.3 N.sub.4 O.sub.6 SNa                     C84 155-157                                                                             C.sub.20 H.sub.17 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                                                  C 43.41                                                                            3.10                                                                             10.13                                                                 F 42.65                                                                            3.30                                                                             9.19                                C85 69-74 C.sub.17 H.sub.14 ClF.sub.3 N.sub.4 O.sub.5 S.sub.2                 C86 Solid C.sub.19 H.sub.20 ClF.sub.3 N.sub.4 O.sub.5                         C87 Solid C.sub.23 H.sub.24 ClF.sub.3 N.sub.4 O.sub.5 S                                                         C 49.24                                                                            4.31                                                                             9.99                                                                  F 46.40                                                                            4.21                                                                             8.63                                C88 Solid C.sub.19 H.sub.17 Cl.sub.2 FN.sub.4 O.sub.5 S                       C89 Solid C.sub.18 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5                         C90 168-172                                                                             C.sub.21 H.sub.20 ClF.sub.3 N.sub.4 O.sub.7 S                       C91 Solid C.sub.21 H.sub.19 ClF.sub.3 N.sub.4 O.sub.7 SNa                     C92 Solid C.sub.20 H.sub.17 ClF.sub.3 N.sub.4 O.sub.5 SNa                     C93 173-179                                                                             C.sub.21 H.sub.18 ClF.sub.3 N.sub.4 O.sub.7 S                       C94 65-70 C.sub.19 H.sub.15 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                C95 110   C.sub.19 H.sub.15 BrClF.sub.3 N.sub.4 O.sub.5 S                                                       C 39.09                                                                            2.59                                                                             9.60                                                                  F 38.75                                                                            2.66                                                                             9.64                                C97 Solid C.sub.20 H.sub.22 ClF.sub.3 N.sub.4 O.sub.5                         C98 Solid C.sub.21 H.sub.17 ClF.sub.3 N.sub.4 O.sub.7 SNa                     C99 Solid C.sub.20 H.sub.17 BrClF.sub.3 N.sub.4 O.sub.6 S                     C100                                                                              Solid C.sub.20 H.sub.16 BrClF.sub.3 N.sub.4 O.sub.6 SNa                   C101                                                                              Solid C.sub.20 H.sub.15 ClF.sub.3 N.sub.5 O.sub.5 S                                                         C 45.33                                                                            2.85                                                                             13.22                                                                 F 44.83                                                                            2.42                                                                             13.06                               C102                                                                              60-70 C.sub.18 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                                                         C 43.69                                                                            3.67                                                                             11.32                                                                 F 43.24                                                                            4.01                                                                             10.71                               C103                                                                              80-95 C.sub.18 H.sub.18 ClF.sub.3 N.sub.4 O.sub.7 S                       C104                                                                              Oil   C.sub.21 H.sub.24 ClF.sub.3 N.sub.4 O.sub.5                         C105                                                                              Solid C.sub.21 H.sub.20 ClF.sub.3 N.sub.4 O.sub.7 S                       C106                                                                              Solid C.sub.21 H.sub.19 ClF.sub.3 N.sub.4 O.sub.7 SNa                     C107                                                                              170   C.sub.19 H.sub.15 ClF.sub.3 N.sub.5 O.sub.7 S                       C108                                                                              Solid C.sub.18 H.sub.19 ClF.sub.3 N.sub.5 O.sub.4                         C109                                                                              Oil   C.sub.22 H.sub.22 ClF.sub.3 N.sub.4 O.sub.6 S                       C110                                                                              85-90 C.sub.22 H.sub.21 ClF.sub.3 N.sub.4 O.sub.6 SNa                     C111                                                                              Oil   C.sub.19 H.sub.16 ClF.sub.3 N.sub.4 O.sub.6 S                       C112                                                                              174-176                                                                             C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.7 S                       C113                                                                              Oil   C.sub.20 H.sub.17 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 S                C114                                                                              60-70 C.sub.20 H.sub.16 Cl.sub.2 F.sub.3 N.sub.4 O.sub.5 SNa              C115                                                                              Solid C.sub.19 H.sub.15 BrClF.sub.3 N.sub.4 O.sub.5 S                     C116                                                                              188-191                                                                             C.sub.20 H.sub.16 ClF.sub.3 N.sub.4 O.sub.7 S                       C117                                                                              >230  C.sub.23 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                       C118                                                                              144-147                                                                             C.sub.21 H.sub.19 Cl.sub.3 F.sub.2 N.sub.4 O.sub.7 S                C119                                                                              211-212                                                                             C.sub.20 H.sub.18 ClF.sub.3 N.sub.4 O.sub.7 S                       C120                                                                              Solid C.sub.20 H.sub.17 ClF.sub.3 N.sub.4 O.sub.7 SNa                     C121                                                                              Solid C.sub.20 H.sub.17 ClF.sub.3 N.sub.4 O.sub.7 SNa                     C122                                                                              105-110                                                                             C.sub.21 H.sub.20 Cl.sub.2 F.sub.2 N.sub.4 O.sub.7 S                C123                                                                              163-166                                                                             C.sub.21 H.sub.20 BrF.sub.3 N.sub.4 SO.sub.7                        C124                                                                              Solid C.sub.21 H.sub.21 ClF.sub.3 N.sub.5 O.sub.5 S                       C125                                                                              Solid C.sub.20 H.sub.15 ClF.sub.6 N.sub.4 O.sub.6 S                       C126                                                                              Solid C.sub.20 H.sub.17 ClF.sub.3 N.sub.5 O.sub.7 S                       C127                                                                              Solid C.sub.28 H.sub.34 ClF.sub.3 N.sub.4 F.sub.3 O.sub.5 S               C128                                                                              Solid C.sub.28 H.sub.33 ClF.sub.3 N.sub.4 O.sub.5 SNa                     C129                                                                              147-149                                                                             C.sub.19 H.sub.16 ClF.sub.3 N.sub.4 O.sub.6 S                                                         C 43.81                                                                            3.10                                                                             10.76                                                                 F 44.31                                                                            3.26                                                                             10.54                               C130                                                                              Solid C.sub.19 H.sub.15 ClF.sub.3 N.sub.4 O.sub.6 SNa                     C131                                                                              198-201                                                                             C.sub.23 H.sub.22 ClF.sub.3 N.sub.4 O.sub.6 S                                                         C 48.05                                                                            3.86                                                                             9.74                                                                  F 47.11                                                                            3.89                                                                             9.34                                C132                                                                              Solid C.sub.20 H.sub.14 ClF.sub.6 N.sub.4 O.sub.6 SNa                     C133                                                                              Solid C.sub.20 H.sub.15 BrF.sub.6 N.sub.4 O.sub.6 S                       C134                                                                              65-68 C.sub.20 H.sub.17 ClF.sub.4 N.sub.4 O.sub.6 S                       C135                                                                              68-72 C.sub.20 H.sub.17 ClF.sub.4 N.sub.4 O.sub.6 S                       C136                                                                              Solid C.sub.21 H.sub.20 ClF.sub.3 N.sub.4 O.sub.6 S                       C137                                                                              130-134                                                                             C.sub.20 H.sub.17 ClF.sub.4 N.sub.4 O.sub.3                         C138                                                                              136-140                                                                             C.sub.23 H.sub.18 ClF.sub.3 N.sub.4 O.sub.5 S                       C139                                                                              Solid C.sub.21 H.sub.19 ClF.sub.3 N.sub.4 O.sub.6 SNa                     C140                                                                              150-153                                                                             C.sub.23 H.sub.22 ClF.sub.3 N.sub.4 O.sub.4                         C141                                                                              160-164                                                                             C.sub.23 H.sub.22 BrF.sub.3 N.sub.4 O.sub.6 S                       C143                                                                              145-147                                                                             C.sub.23 H.sub.24 ClF.sub.3 N.sub.4 O.sub.7 S                       C147                                                                              148-152                                                                             C.sub.21 H.sub.19 ClF.sub.3 N.sub.5 O.sub.7 S                       C156                                                                              95-98 C.sub.23 H.sub.22 Cl.sub.2 F.sub.2 N.sub.4 O.sub.6 S                C161                                                                              oil   C.sub.22 H.sub.20 ClF.sub.3 N.sub.4 O.sub.5                         C179                                                                              124-127                                                                             C.sub.27 H.sub.18 ClF.sub.3 N.sub.4 O.sub.7 S                       C180                                                                              146-149                                                                             C.sub. 19 H.sub.14 Cl.sub.3 F.sub.3 N.sub.4 O.sub.3                                                   C 44.77                                                                            2.77                                                                             10.99                                                                 F 44.97                                                                            2.79                                                                             10.61                               C204                                                                              solid C.sub.21 H.sub.20 Cl.sub.2 F.sub.2 N.sub.4 O.sub.7 S                C205                                                                              solid C.sub.21 H.sub.20 Br.sub.2 F.sub.2 N.sub.4 O.sub.7 S                C206                                                                              100-105                                                                             C.sub.23 H.sub.17 ClF.sub.3 N.sub.4 O.sub.5 SNa                     C207                                                                              115-121                                                                             C.sub.20 H.sub.16 ClF.sub.4 N.sub.4 O.sub.6 SNa                     C208                                                                              161-165                                                                             C.sub.22 H.sub.20 ClF.sub.3 N.sub.4 O.sub.6 S                       C209                                                                              oil   C.sub.22 H.sub.18 ClF.sub.3 N.sub.4 O.sub.6 S                       C232                                                                              solid C.sub.22 H.sub.17 ClF.sub.3 N.sub.4 O.sub.6 SNa                     C234                                                                              87    C.sub.22 H.sub.18 BrF.sub.3 N.sub.4 O.sub.6 S                                                         C 43.79                                                                            3.01                                                                             9.29                                                                  F 42.95                                                                            2.87                                                                             8.96                                C239                                                                              50-53 C.sub.23 H.sub.20 Cl.sub.2 F.sub.2 N.sub.4 O.sub.6 S                C240                                                                              solid C.sub.23 H.sub.20 ClF.sub.3 N.sub.4 O.sub.6 S                                                         C 48.22                                                                            3.52                                                                             9.78                                                                  F 48.17                                                                            3.39                                                                             9.14                                C241                                                                              84-89 C.sub.23 H.sub.24 Cl.sub.2 F.sub.2 N.sub.4 O.sub.6 S                C245                                                                              55-60 C.sub.23 H.sub.18 F.sub.6 N.sub.4 O.sub.6 S                         C267                                                                              solid C.sub.22 H.sub.19 ClF.sub.3 N.sub.4 O.sub.6 SNa                     C268                                                                              solid C.sub.18 H.sub.17 ClF.sub.3 N.sub.5 O.sub.6 S                                                         C 41.27                                                                            3.27                                                                             13.37                                                                 F 40.34                                                                            3.10                                                                             12.80                               C269                                                                              solid C.sub.22 H.sub.18 Cl.sub.2 F.sub.2 N.sub.4 O.sub.6 S                                                  C 45.93                                                                            3.15                                                                             9.74                                                                  F 45.25                                                                            3.08                                                                             9.19                                C291                                                                              75-80 C.sub.23 H.sub.21 Cl.sub.2 F.sub.3 N.sub.4 O.sub.6 S                C292                                                                              solid C.sub.23 H.sub.21 ClF.sub.3 N.sub.4 O.sub.6 SK                      C293                                                                              solid C.sub.26 H.sub.31 ClF.sub.3 N.sub.5 O.sub.6 S                       C294                                                                              88-90 C.sub.24 H.sub.22 F.sub.6 N.sub.4 O.sub.6 S                         C295                                                                              solid C.sub.23 H.sub.22 ClF.sub.3 N.sub.4 O.sub.6 S                                                         C 48.05                                                                            3.86                                                                             9.74                                                                  F 47.21                                                                            3.95                                                                             9.31                                C296                                                                              solid C.sub.23 H.sub.21 ClF.sub.3 N.sub.4 O.sub.6 SNa                     __________________________________________________________________________

    TABLE 3      Preemergence Herbicidal Activity       Compound No. C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 Rate     (kg/ha) 2.0 1.0 2.0 2.0 2.0 2.0 1.0 2.0 1.0 1.0 1.0 1.0 2.0 2.0 Species     % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C     % K % C % K % C % K % C % K % C % K      % C                                    Cotton 70 100 100 40 100 100 100     90 80 100 100 100 100 100 Soybean 40 100 40 0 100 90 10 100 90 90 100     100 100 100 Field Corn 60 100 80 0 100 100 100 100 100 20 100 100 90 100     Rice 20 100 80 0 100 100 40 100 90 80 100 100 100 100 Wheat 20 100 90 40     100 100 30 100 100 70 100 100 90 100 Field Bindweed 100 100 100 80 100     100 100 100 100 100 100 100 100 100 Morningglory 100 100 100 90 100 90     100 100 100 100 100 100 100 100 Velvetleaf 100 100 100 100 100 100 100     100 100 100 100 100 100 100 Barnyardgrass 80 100 100 90 100 100 100 100     100 100 100 100 100 100 Green Foxtail 90 100 100 90 100 100 90 100 100     100 100 100 100 100 Johnsongrass 80 100 100 50 100 100 90 100 100 90 100     100 100 100 Yellow Nutsedge 80 100 100 50 100 100 100 90 80 60 100 100     100 100       Compound No. C15 C16 C17 C18 C19 C20 C21 C22 C23 C24 C25 C26 C32 C38     Rate (kg/ha) 2.0 2.0 2.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 2.0 1.0 1.0 1.0     Species % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C     % K % C % K % C % K % C % K % C % K % C % K      % C                             Cotton 100 100 100 100 100 100 100 100     30 40 100 100 100 90 Soybean 100 100 100 0 20 80 90 100 50 10 30 100 40     100 Field Corn 100 100 100 70 100 50 100 100 90 80 70 100 20 100 Rice     100 100 90 80 60 30 80 100 20 30 60 90 50 100 Wheat 100 100 90 50 40 10     100 100 70 0 30 100 10 100 Field Bindweed 100 100 100 80 80 100 100 100     100 90 100 100 100 100 Morningglory 100 100 100 100 100 100 100 100 100     100 100 100 100 100 Velvetleaf 100 100 100 100 100 100 100 100 100 90     100 100 100 100 Barnyardgrass 100 100 100 100 100 100 100 100 100 80 100     100 100 100 Green Foxtail 100 100 100 100 100 100 100 100 100 100 90 100     80 100 Johnsongrass 100 100 100 90 90 40 100 100 100 70 70 100 80 100     Yellow Nutsedge100 100 100 90 80 10 80 100 40 30 80 100 40 ND       Compound No. C42 C43 C59 C69 C70 C71 C72 C73 C74 C75 C76 C77 C78 C79     Rate (kg/ha) 1.0 1.0 1.0 0.5 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0     Species % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C     % K % C % K % C % K % C % K % C% K % C % K      % C                             Cotton 90 100 100 40 100 100 100 80 100     90 60 95 80 50 Soybean 70 70 50 10 20 50 50 30 80 30 30 40 40 0 Field     Corn 40 70 70 30 30 50 60 30 0 50 20 30 50 10 Rice 60 90 80 30 70 40 30     40 40 60 30 70 50 50 Wheat 70 70 40 0 20 40 20 50 30 40 20 60 40 20     Field Bindweed 100 100 100 90 100 100 100 100 90 100 100 100 100 80     Morningglory 100 100 100 80 100 100 100 100 100 100 100 100 100 100     Velvetleaf 100 100 100 100 100 100 100 100 100 100 100 100 100 100     Barnyardgrass 100 100 100 20 20 90 100 90 85 95 100 100 100 80 Green     Foxtail 100 100 100 20 0 40 95 100 100 95 70 100 90 100 Johnsongrass 60     95 100 40 80 60 90 80 70 80 40 95 40 80 Yellow Nutsedge 70 100 70 70 90     40 60 20 20 30 30 50 30 20       Compound No. C80 C81 C82 C83 C84 C85 C86 C87 C88 C89 C90 C91 C92 C93     Rate (kg/ha) 1.0 1.0 1.0 1.0 1.0 1.0 2.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0     Species % K % C % K % C % K % C % K % C % K % C % K % C 5 K % C % K % C     % K % C % K % C % K % C % K % C % K % C % K      % C                            Cotton 60 100 100 95 10 100 100 30 0 90     100 100 100 20 Soybean 20 100 10 95 0 30 70 20 10 30 100 90 30 0 Field     Corn 0 50 20 20 10 95 100 10 10 60 80 80 20 30 Rice 20 50 30 40 20 80 90     40 0 90 80 90 40 50 Wheat 30 100 20 30 0 80 90 10 0 80 70 50 30 10 Field     Bindweed 100 100 100 100 30 100 100 100 0 100 100 100 100 80 Morningglory      100 100 100 100 100 100 100 100 0 100 100 100 100 80 Velvetleaf 100 100     100 100 90 100 100 100 10 100 100 100 100 100 Barnyardgrass 95 100 95 95     10 100 100 95 40 100 100 100 100 100 Green Foxtail 100 100 100 90 30 100     100 0 0 100 100 100 100 0 Johnsongrass 95 100 95 80 30 100 100 30 10 95     100 95 80 30 Yellow Nutsedge 0 80 10 20 ND ND ND ND ND ND ND ND ND     ND      Compound No. C94 C95 C97 C98 C99 C100 C101 C102 C103 C104 C105     C106 C107 C108 Rate (kg/ha) 1.0 1.0 1.0 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5     0.5 0.5 0.5 Species % K % C % K % C % K % C % K % C% K % C % K % C % K %     C % K % C % K  % C % K % C % K % C % K % C % K % C % K      % C                 Cotton 80 100 100 100 80 80 95 30 30 30 100 100 90     100 Soybean 20 60 20 30 70 50 30 20 10 10 95 90 10 95 Field Corn 20 20     70 40 30 60 10 50 30 90 70 30 20 100 Rice 20 30 80 20 20 60 20 80 50 80     95 90 40 95 Wheat 0 10 70 20 10 20 10 50 30 80 50 30 0 95 Field Bindweed     100 100 100 100 100 100 90 20 40 100 100 100 80 90 Morningglory 100 100     100 100 100 100 100 80 60 90 100 100 95 100 Velvetleaf 100 100 100 100     100 100 100 100 100 100 100 100 100 100 Barnyardgrass 60 40 100 90 100     70 60 100 95 95 100 100 40 80 Green Foxtail 50 50 100 80 100 80 40 100     100 100 100 100 0 100 Johnsongrass 60 60 90 95 80 80 50 80 80 95 100 100     50 100 Yellow Nutsedge ND ND ND ND ND ND ND ND ND ND ND ND ND ND       Compound No. C109 C110 C111 C112 C113 C114 C115 C116 C117 C118 C119     C120 C121 C122 Rate (kg/ha) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5     0.5 0.5 0.5 Species % K % C % K % C% K % C % K % C % K % C % K % C % K %     C % K % C % K % C % K % C % K % C % K % C % K % C % K      % C                  Cotton 70 30 20 90 50 30 80 95 50 20 50 70 95 70     Soybean 90 95 40 40 0 0 30 0 95 0 30 20 20 50 Field Corn 100 100 10 0 10     10 10 10 10 10 10 10 20 40 Rice 95 90 70 20 20 20 10 20 30 0 30 20 30 0     Wheat 100 100 50 10 10 10 30 10 0 10 30 10 10 10 Field Bindweed 95 100     70 100 100 90 100 90 100 80 100 100 100 100 Morningglory 100 100 70 90     90 95 100 95 100 50 100 90 90 80 Velvetleaf 100 100 90 100 100 100 100     100 100 50 100 100 100 100 Barnyardgrass 100 100 100 40 50 70 50 80 40     10 50 80 70 70 Green Foxtail 100 100 100 80 30 70 90 40 80 10 0 0 20 50     Johnsongrass 100 100 70 95 30 70 90 80 20 10 70 70 90 100 Yellow     Nutsedge ND ND ND ND ND ND ND ND ND ND ND ND ND ND       Compound No. C123 C124 C125 C140 C147 C161 C179 C180 C204 C205 C206     C207 C208  C232 C234 C235 C236 C237 C238 C239 C241 C242 C245 C269 Rate     (kg/ha) 0.25 0.5 0.5 0.5 0.5 0.5 1.0 0.5 0.5 0.5 0.5 0.5 0.5 0.25 0.25     0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.25 0.25 Species % K % C % K % C % K % C %     C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C %     C % C % C       Cotton 50 20 20 60 20 50 30 20 60 30 95 60 30 20 10 20 10 30 40 90 10     80 10 10 Soybean 50 60 30 30 30 0 10 0 50 10 30 20 70 5 20 50 10 70 30     50 20 100 0 0 Field Corn 0 70 10 20 70 0 10 0 30 20 10 0 80 5 0 0 10 95     20 95 95 20 0 0 Rice 60 80 10 60 30 50 20 30 30 10 70 50 80 5 0 10 50 90     40 80 80 40 0 0 Wheat 10 60 10 70 40 40 30 30 0 0 10 20 100 0 0 20 0 30     80 70 20 0 0 Field Bindweed 100 100 80 70 20 50 80 70 100 50 100 100 70     -- -- 80 40 20 95 70 10 100 -- -- Morningglory 100 95 90 100 100 100 80     60 100 95 100 100 95 20 60 100 20 95 100 80 40  100 20 0 Wild Mustard               90 90 -- -- -- -- -- -- -- 70 0 Velvetleaf 100 100 100 100 ND     100 100 ND 100 100 100 100 100 100 90 100 70 100 100 100 100 100 100 95     Barnyardgrass 100 100 30 95 50 100 80 60 90 10 100 100 100 30 0 0 50 100     80 100 95 70 0 0 Green Foxtail 10 100 50 95 100 80 70 100 20 20 80 100     95 10 0 90 50 100 90 100 90 100 0 0 Johnsongrass 100 100 10 95 60 95 70     60 90 50 100 60 100 0 10 10 95 60 10 95 95 60 0 0 Yellow Nutsedge ND ND     ND

    TABLE 4      Postemergence Herbicidal Activity Compound No. C1   C2   C3   C4   C5   C     6   C7   C8   C9   C10   C11   C12    C13   C14   Rate (kg/ha) 2.0   1.0       2.0   2.0   2.0   2.0   1.0   2.0   1.0   1.0   1.0   1.0   2.0   2.0        % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K %     C % K % C % K % C % K % C % K % C % K      % C                                  Species Cotton 100 100 100 70 100     100 100 100 90 100 100 100 100 100 Soybean 30 90 40 40 90 90 60 90 80     100 90 90 80 100 Field Corn 70 100 100 40 100 100 50 90 80 60 100 100     100 100 Rice 20 100 70 50 100 100 80 80 50 60 100 100 100 70 Wheat 0 100     40 30 100 100 10 80 60 60 100 100 100 100 Field Bindweed 100 100 90 100     100 100 100 100 90 60 90 100 100 100 Morningglory 100 100 100 90 100 100     100 100 80 100 100 100 100 100 Velvetleaf 100 100 100 100 100 100 100     100 100 100 100 100 100 100 Barnyardgrass 100 100 100 90 100 100 100 60     100 100 100 100 100 100 Green Foxtail 100 100 100 90 100 100 100 100 100     100 100 100 100 100 Johnsongrass 80 100 90 40 90 100 90 80 90 80 90 100     100 100 Yellow Nutsedge 60 100 30 20 100 100 80 60 20 10 100 100 100     100   Compound No. C15   C16   C17   C18   C19   C20   C21   C22   C23     C24   C25   C26   C32   C38   Rate (kg/ha) 2.0   2.0   2.0   1.0   1.0     1.0   1.0   1.0   1.0   1.0   2.0   1.0   1.0   1.0    % K % C % K % C %     K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C %     K % C % K % C % K      % C                                                      Species Cotton     100 100 100 100 100 100 100 100 100 50 100 100 100 100 Soybean 90 100     100 40 40 100 100 100 80 20 70 80 80 100 Field Corn 90 100 100 30 20 0     100 100 80 20 60 100 20 100 Rice 50 90 100 10 10 20 60 80 30 10 50 90 50     100 Wheat 100 100 100 100 100 100 100 100 90 10 60 90 50 100 Field     Bindweed 100 100 90 100 100 100 100 100 100 100 100 100 100 70 Morningglo     ry 100 100 100 100 100 100 100 100 80 90 100 100 100 100 Velvetleaf 100     100 100 100 100 100 100 100 100 100 100 100 100 100 Barnyardgrass 100     100 100 100 100 100 100 100 100 80 100 100 100 100 Green Foxtail 100 100     100 100 100 100 100 100 100 100 100 100 80 100 Johnsongrass 90 100 50 90     100 40 100 100 100 60 100 90 40 90 Yellow Nutsedge 90 100 100 100 60 10     80 80 40 0 70 90 20 ND       Compound No. C42   C43   C59   C69   C70   C71   C72   C73   C74   C75       C76   C77   C78   C79   Rate (kg/ha) 1.0   1.0   1.0   0.5   1.0   1.0       1.0   1.0   1.0   1.0   1.0   1.0   1.0   1.0    % K % C % K % C % K %     C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K %     C % K % C % K      % C                                                          Species     Cotton 100 100 100 100 90 100 100 100 85 95 95 100 100 100 Soybean 100     90 80 50 60 60 70 85 90 90 80 80 100 50 Field Corn 100 100 80 80 40 60     50 30 40 100 70 100 100 20 Rice 60 50 40 60 30 40 60 60 60 40 40 30 30     20 Wheat 90 95 80 90 40 95 30 80 50 40 30 100 90 40 Field Bindweed 100     100 100 100 100 100 100 100 95 100 100 100 100 50 Morningglory 95 100     100 100 100 100 100 100 100 100 95 100 100 60 Velvetleaf 100 100 100 100     100 100 100 100 100 100 100 100 100 100 Barnyardgrass 95 100 100 100 100     100 100 90 100 95 95 95 100 100 Green Foxtail 100 100 100 50 30 100 60     90 85 100 95 100 90 95 Johnsongrass 95 100 95 60 70 50 50 70 50 80 40 70     60 80 Yellow Nutsedge 40 95 100 50 40 20 60 30 30 10 20 30 20 70       Compound No. C80   C81   C82   C83   C84   C85   C86   C87   C88   C89       C90    C91   C92   C93   Rate (kg/ha) 1.0   1.0   1.0   1.0   1.0     1.0   2.0   1.0   1.0   1.0   1.0   1.0   1.0   1.0    % K % C % K % C %     K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C %     K % C % K % C % K      % C                                                      Species Cotton     100 100 100 100 80 100 100 90 10 90 100 100 100 100 Soybean 80 100 80     100 40 90 80 100 30 90 100 100 90 70 Field Corn 40 80 100 95 40 95 100     100 20 100 95 100 100 70 Rice 10 90 70 60 20 95 100 50 10 70 60 90 70 30     Wheat 40 95 90 90 30 80 100 60 10 100 100 100 80 80 Field Bindweed 100     100 100 100 20 95 100 100 10 95 100 100 100 70 Morningglory 100 100 100     100 90 100 100 100 20 100 100 100 100 95 Velvetleaf 100 100 100 100 100     100 100 100 20 100 100 100 100 100 Barnyardgrass 40 100 100 100 95 100     100 100 20 100 100 100 100 100 Green Foxtail 100 100 100 100 30 100 100     80 50 100 100 100 80 95 Johnsongrass 40 100 100 95 20 90 100 30 30 80     100 100 70 30 Yellow Nutsedge 20 20 0 60 ND ND ND ND ND ND ND ND ND     ND     Compound No. C94   C95   C97   C98   C99   C100   C101   C102     C103   C104   C105   C106   C107   C108   Rate (kg/ha) 1.0   1.0   1.0     0.5   0.5   0.5   0.5   0.5   0.5   0.5   0.5   0.5   0.5   0.5    % K %     C % K % C % K  % C % K % C % K % C % K % C % K % C % K % C % K % C % K %     C % K % C % K % C % K % C % K      % C                                          Species Cotton 100 100 95     90 90 100 100 100 100 80 100 100 100 100 Soybean 80 95 95 70 100 100 60     50 30 80 100 100 60 100 Field Corn 50 95 100 70 100 100 50 60 30 90 95     100 60 100 Rice 30 70 95 70 40 40 20 70 40 70 95 95 20 95 Wheat 40 100     100 90 100 100 40 95 30 90 100 100 20 100 Field Bindweed 95 100 95 100     100 100 90 90 95 50 100 100 100 100 Morningglory 100 100 100 100 100 100     90 100 95 90 100 100 100 100 Velvetleaf 100 100 100 100 100 100 100 95     100 100 100 100 100 100 Barnyardgrass 80 90 95 95 100 100 30 60 60 95     100 100 95 100 Green Foxtail 95 100 100 70 90 100 10 100 100 95 100 100     90 100 Johnsongrass 60 70 95 90 100 90 50 70 70 80 100 100 60 100 Yellow     Nutsedge ND ND ND ND ND ND ND ND ND ND ND ND ND ND       Compound No. C109   C110   C111   C112   C113   C114   C115   C116     C117   C118   C119   C120   C121   C122   Rate (kg/ha) 0.5   0.5   0.5     0.5   0.5   0.5   0.5   0.5   0.5   0.5   0.5   0.5   0.5   0.5    % K %     C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K % C % K %     C % K % C % K % C % K % C % K      % C                                          Species Cotton 95 80 40 90     80 95 20 100 100 40 95 80 100 95 Soybean 95 100 50 90 40 50 30 60 100 95     95 95 80 80 Field Corn 80 90 20 40 30 30 30 40 100 100 40 60 10 60 Rice     80 80 20 20 $0 $0 10 20 0 10 10 10 20 10 Wheat 95 95 70 90 30 30 30 60     95 60 90 100 100 100 Field Bindweed 100 100 60 100 100 100 10 80 100 95     100 100 100 95 Morningglory 100 100 100 100 100 100 30 100 100 80 100     100 100 100 Velvetleaf 100 100 100 100 100 100 20 100 100 100 100 100     100 100 Barnyardgrass 100 100 100 95 30 70 20 70 100 60 50 50 80 100     Green Foxtail 100 100 100 100 80 90 30 70 100 40 70 20 30 80 Johnsongrass      100 100 95 95 40 30 30 80 70 20 60 40 80 80 Yellow Nutsedge ND ND ND ND     ND ND ND ND ND ND ND ND ND ND       Compound No. C123   C124   C125   C140   C147 C161 C179 C180 C204 C205 C     206 C207 C208 C232 C234 C235 C236 C237 C238 C239 C241 C242 C245 C269     Rate (kg/ha) 0.25   0.5   0.5   0.5  0.5  0.5  1.0  0.5  0.5  0.5  0.5     0.5  0.5  0.25 0.25 0.5  0.5  0.5   0.5  0.5  0.5  0.5  0.25 0.25  % K %     C % K % C % K % C % C % C % C % C % C % C % C % C % C % C % C % C % C %     C % C % C % C % C % C % C % C       Species Cotton 100 100 100 100 30 70 80 100 100 90 100 100 70 90 100     100 60 100 90 95 80 100 100 95 Soybean 100 100 100 50 80 40 80 60 95 60     80 80 95 90 90 95 50 90 100 80 70 100 80 50 Field Corn 90 100 100 60 70     60 60 70 100 100 80 50 40 20 50 50 40 60 100 90 50 80 20 40 Rice 90 70 0     60 70 30 30 30 50 30 50 60 60 40 10 20 40 80 70 90 50 70 10 10 Wheat 100     100 100 95 95 40 40 40 100 90 95 90 90 80 80 40 40 80 95 80 50 80 80 50     Field Bindweed 100 100 100 30 60 90 100 70 100 70 100 95 100 -- -- 100     30 90 100 95 95 100 -- -- Morningglory 100 100 100 90 95 100 70 90 100     90 100 100 100 100 100 100 70 100 100 100 95 100 90 80 Wild Mustard             100 100 -- -- -- -- -- -- -- 100 80 Velvetleaf 100 100 100 100     95 100 100 95 100 100 100 100 100 100 100 100 90 100 100 100 100 100 100     100 Barnyardgrass 95 100 95 90 95 90 90 90 80 70 100 80 100 50 40 50 60     95 90 95 95 50 30 30 Green Foxtail 95 100 95 90 95 100 90 50 80 90 90 80     100 100 20 95 70 95 95 100 100 95 80 30 Johnsongrass 95 95 90 60 70 90     40 40 90 90 90 70 100 20 50 20 80 95 95 100 100 95 50 50 Yellow Nutsedge     ND ND ND       Paddy Rice Test Compound No. C25 C99 C123 C136 C170 C184 Rate (kg/ha)     0.0625 0.03125 0.03125 0.03125 0.03125 0.03125  % C % C % C % C % C %     C    Species Rice-Mars 0 20 10 20 0  0 Rice-Labelle  0 0 20 10 0  10     Hemp Sesbania 70 60 50 50 30* 50 Flatsedge Rice 95 90 95 100 100  80     Barnyardgrass 70 40 90 80 70* 50 Green Sprangletop 100 95 95 100 10*     *Data marked with asterisk were obtained in a separate test in the absenc     of the rice crop.

What is claimed is:
 1. A herbicidal compound of the formula ##STR242##in which X is Br, Cl, F or CF₃ ;Y is Br, Cl, F, CH₃, CH₂ F, or a radicalof the formula R⁸ OCH₂ --, R⁸ SCH₂ --, R⁸ SOCH₂ -- or R⁸ SO₂ CH₂ --where R⁸ is C₁ -C₃ alkyl, C₂ -C₅ alkenyl, C₃ -C₅ alkynyl, phenyl, orphenyl substituted with halogen or with alkyl or haloalkyl of less than6 carbon atoms; R³ is alkylene or haloalkylene of less than 6 carbonatoms; R¹ is halogen, alkyl of 1 to 5 carbon atoms, haloalkyl of 1 to 5carbon atoms, alkoxyalkyl of 2 to 6 carbon atoms, cyanoalkyl of 2 to 6carbon atoms, benzyl, alkylthio of 1 to 3 carbon atoms, alkylsulfinyl of1 to 3 carbon atoms, alkylsulfonyl of 1 to 3 carbon atoms, oralkylthioalkyl, alkylsulfinylalkyl, or alkylsulfonylalkyl of 1 to 3carbon atoms independently with respect to each alkyl; R² is alkyl of 1to 5 carbon atoms, haloalkyl of 1 to 5 carbon atoms, alkenyl of 2 to 5carbon atoms, alkynyl of 3 to 5 carbon atoms, cyanomethyl, cyanoethyl,thiocyanomethyl, or a group of the formula -alkylene-Y¹ -R⁵ in whichsaid alkylene group has 1 to 5 carbon atoms, Y¹ is oxygen or S(O)_(r) inwhich r is 0-2, and R⁵ is alkyl of 1 to 5 carbon atoms, alkenyl of 2 to5 carbon atoms, or alkynyl of 3 to 5 carbon atoms; R₆ is an arylsulfonylgroup wherein the aryl is selected from the group consisting of phenyl,isoxazolyl, thienyl, benzofuran, dihydrobenzofuran, naphthyl,benzodioxole, anthraquinone, and 1,4-naphthoquinone, said group beingunsubstituted or having one or more substituents selected from halogen,nitro, amino, fluorosulfonyl, alkyl, haloalkyl, aminoalkyl,dialkylaminoalkyl, haloalkoxy, alkoxy, alkenyloxy, haloalkenyloxy,alkynyloxy, cyanoalkoxy, epoxyalkoxy, dialkylaminoalkoxy, alkoxyalkoxy,alkoxyalkylthio, cyano, aminocarbonyloxy, alkylaminocarbonyloxy,dialkylaminocarbonyloxy, acylamino, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, and hydroxycarbonyl in whichany alkyl, alkenyl or alkynyl moiety has less than 6 carbon atoms; andR₇ is hydrogen, a salt forming group, cycloalkyl and alkyl, alkenyl, oralkynyl having less than 6 carbon atoms.
 2. A compound as in claim 1 inwhich said arylsulfonyl is a halophenyl, alkoxyphenyl, or alkylphenyl ora 2,3-dihydrobenzofuranyl.
 3. The compound of claim 1 in which X is F, Yis Cl, R³ is --CH(CH₃)--, R² is CHF₂, and R¹ is CH₃.
 4. A compound as inclaim 2 in which the sulfonamide is a2,3-dihydro-2,2-dimethylbenzofuranylsulfonamide.
 5. The compound ofclaim 4 in which X is F, Y is Cl, R³ is --CH(CH₃)--, R² is CHF₂, and R¹is CH₃.
 6. An herbicidal composition comprising an herbicidallyeffective amount of the compound of claim 2 in admixture with a suitablecarrier.
 7. A method for controlling undesired plant growth whichcomprises applying to the locus where control is desired an herbicidallyeffective amount of the composition of claim
 6. 8. An herbicidalcomposition comprising an herbicidally effective amount of the compoundof claim 2 in admixture with a suitable carrier.
 9. A method forcontrolling undesired plant growth which comprises applying to the locuswhere control is desired an herbicidally effective amount of thecomposition of claim
 8. 10. A compound as in claim 1 in which the arylof said arylsulfonylamide is phenyl or phenyl substituted with halogen,nitro, amino, fluorosulfonyl, alkyl, haloalkyl, aminoalkyl,dialkylaminoalkyl, haloalkoxy, alkoxy, alkenyloxy, haloalkenyloxy,alkynyloxy, cyanoalkoxy, epoxyalkoxy, dialkylaminoalkoxy, alkoxyalkoxy,alkoxyalkylthio, cyano, aminocarbonyloxy, alkylaminocarbonyloxy,dialkylaminocarbonyloxy, acylamino, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl or hydroxycarbonyl.
 11. Aherbicidal composition comprising a herbicidally effective amount of thecompound of claim 10 in admixture with a suitable carrier.
 12. A methodof controlling undesired plant growth which comprises applying to thelocus where control is desired a herbicidally effective amount of thecomposition of claim 11.